Malononitrile compounds and their use as pesticides

ABSTRACT

The present invention relates to malononitrile compounds of formula                  
 
wherein R 1  and R 2  are the same or different and independently C 1 –C 5  (halo)alkyl, C 1 –C 5  (halo)alkyloxy, C 2 –C 5  (halo)alkenyl, C 2 –C 5  (halo)alkynyl, hydrogen, or cyano; R 3  is C 1 –C 3  haloalkyl, C 2 –C 4  haloalkenyl, or C 2 –C 4  haloalkynyl; m is an integer of 1 to 3; R 5  is halogen, cyano, nitro, C 1 –C 4  (halo)alkyl, or the like; n is an integer of 0 to 4, with the proviso that when n is 2 or more, then R 5 &#39;s are the same or different from each other; R 6  is hydrogen, halogen, cyano, nitro, C 1 –C 4  (halo)alkyl, or the like; as well as pesticide compositions containing these compounds as active ingredients. The present invention makes it possible to effectively control pests such as insect pests, acarine pests, and nematode pests.

TECHNICAL FIELD

The present invention relates to malononitrile compounds and their useas pesticide compositions.

BACKGROUND ART

Against pests such as insect pests, acarine pests, and nematode pests,various pesticide compositions have been used so far for their control.The conditions of pesticide compositions required have drastically beenchanged, including the care of their effects on the environment and theacquisition of drug resistance by pests to be controlled. Under suchcircumstances, there have been great demands for the development of newpesticide compositions.

DISCLOSURE OF INVENTION

The present inventors have extensively studied to find compounds havingexcellent pest controlling activity. As a result, they have found thatthe malononitrile compounds of formula (Y) as depicted below haveexcellent controlling activity against pests such as insect pests,acarine pests, and nematode pests, thereby reaching the presentinvention.

That is, the present invention provides malononitrile compounds offormula (Y):

(hereinafter referred to as the present compound(s))wherein R¹ and R² are the same or different and independently C₁–C₅(halo)alkyl, C₁–C₅ (halo)alkyloxy, C₂–C₅ (halo)alkenyl, C₂–C₅(halo)alkynyl, hydrogen, or cyano;

R³ is C₁–C₃ haloalkyl, C₂–C₄ haloalkenyl, or C₂–C₄ haloalkynyl;

m is an integer of 1 to 3;

R⁵ is halogen, cyano, nitro, C₁–C₄ (halo)alkyl, C₂–C₄ (halo)alkenyl,C₂–C₄ (halo)alkynyl, C₁–C₄ (halo)alkyloxy, C₁–C₄ (halo)alkylthio, C₁–C₄(halo)alkylsulfinyl, C₁–C₄ (halo)alkylsulfonyl, C₁–C₄(halo)alkylcarbonyl, C₁–C₄ (halo)alkyloxycarbonyl, C₁–C₄(halo)alkylcarbonyloxy, benzyloxy, phenyloxy, or phenylthio, in whichthe phenyloxy and phenylthio groups may optionally be substituted withhalogen or C₁–C₃ alkyl;

n is an integer of 0 to 4;

R⁶ is hydrogen, halogen, cyano, nitro, C₁–C₄ (halo)alkyl, C₂–C₄(halo)alkenyl, C₂–C₄ (halo)alkynyl, C₁–C₄ (halo)alkyloxy, C₁–C₄(halo)alkylthio, C₁–C₄ (halo)alkylsulfinyl, C₁–C₄ (halo)alkylsulfonyl,C₁–C₄ (halo)alkylcarbonyl, C₁–C₄ (halo)alkyloxycarbonyl, C₁–C₄(halo)alkylcarbonyloxy, benzyloxy, phenyloxy, or phenylthio, in whichthe phenyloxy and phenylthio groups may optionally be substituted withhalogen or C₁–C₃ alkyl;

with the proviso that when n is 2 or more, then R⁵'s are the same ordifferent from each other.

The present invention also provides use of the present compounds as apesticide; pesticide compositions comprising the present compounds asactive ingredients; and a pest controlling method comprising applyingthe present compounds to pests or habitats of pests.

MODE FOR CARRYING OUT THE INVENTION

In the definition of substituents as used herein, each group has thefollowing meaning:

The (halo)alkyl group refers to alkyl optionally substituted withhalogen for one or more than one hydrogen atoms.

The (halo)alkyloxy group refers to alkyloxy optionally substituted withhalogen for one or more than one hydrogen atoms.

The (halo)alkenyl group refers to alkenyl optionally substituted withhalogen for one or more than one hydrogen atoms.

The (halo)alkynyl group refers to alkynyl optionally substituted withhalogen for one or more than one hydrogen atoms.

The (halo)alkylthio group refers to alkylthio optionally substitutedwith halogen for one or more than one hydrogen atoms.

The (halo)alkylsulfinyl group refers to alkylsulfinyl optionallysubstituted with halogen for one or more than one hydrogen atoms.

The (halo)alkylsulfonyl group refers to alkylsulfonyl optionallysubstituted with halogen for one or more than one hydrogen atoms.

The (halo)alkylcarbonyl group refers to alkylcarbonyl optionallysubstituted with halogen for one or more than one hydrogen atoms.

The (halo)alkyloxycarbonyl group refers to alkyloxycarbonyl optionallysubstituted with halogen for one or more than one hydrogen atoms.

The (halo)alkylcarbonyloxy group refers to alkylcarbonyloxy optionallysubstituted with halogen for one or more than one hydrogen atoms.

The haloalkyl group refers to alkyl substituted with halogen for atleast one or more hydrogen atoms.

The haloalkenyl group refers to alkenyl substituted with halogen for atleast one or more hydrogen atoms.

The haloalkynyl group refers to alkynyl substituted with halogen for atleast one or more hydrogen atoms.

The term “C1–C10” or the like refers to number of carbon atomsconstituting the alkyl, alkenyl, or alkynyl group in each substituent.For example, C₁–C₄ (halo)alkylcarbonyl means alkylcarbonyl optionallysubstituted with halogen for one or more hydrogen atoms wherein thealkyl part is constituted by C₁–C₄ carbon atoms.

In the present compounds, each group includes specific ones as listedbelow:

The C₁–C₅ (halo)alkyl group represented by R¹ or R² may include methyl,ethyl, propyl, 1-methylethyl, 1,1-dimethylethyl, 2,2-dimethylpropyl,chloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl,2,2,2-trifluoroethyl, and 1,1,2,2-tetrafluoroethyl.

The C₁–C₅ (halo)alkyloxy group represented by R¹ or R² may includemethoxy, ethoxy, 1-methylethoxy, trifluoromethoxy, difluoromethoxy,2,2,2-trifluoroethoxy, and 1,1,2,2-tetrafluoroethoxy.

The C₂–C₅ (halo)alkenyl group represented by R¹ or R² may include vinyl,1-propenyl, 2-propenyl, 2,2-difluorovinyl, and 1,2,2-trifluorovinyl.

The C₂–C₅ (halo)alkynyl group represented by R¹ or R² may includeethynyl, 1-propynyl, 2-propynyl and 3,3,3-trifluoro-1-propynyl.

The C₁–C₃ haloalkyl group represented by R³ may include fluoromethyl,chloromethyl, difluoromethyl, dichloromethyl, trifluoromethyl,trichloromethyl, 1,1-difluoroethyl, pentafluoroethyl,1,1-difluoropropyl, heptafluoropropyl, 2,2,2-trifluoroethyl,3,3,3-trifluoropropyl, and 1,1,2,2-tetrafluoroethyl.

The C₂–C₄ haloalkenyl group represented by R³ may include 1-chlorovinyl,2-chlorovinyl, 1-fluorovinyl, 2-fluorovinyl, 2,2-dichlorovinyl,2,2-dibromovinyl, 2,2-difluorovinyl, 1,2,2-trifluorovinyl,1-(trifluoromethyl)vinyl, 3,3,3-trifluoro-1-propenyl,2,3,3,3-tetrafluoro-1-propenyl, 1,2,3,3,3-pentafluoro-1-propenyl,3,3-difluoro-2-propenyl, 2,3,3-trifluoro-2-propenyl, and3,4,4-trifluoro-3-butenyl.

The C₂–C₄ haloalkynyl group represented by R³ may include3-chloro-2-propynyl and 3,3,3-trifluoro-1-propynyl.

The halogen atom represented by R⁵ or R⁶ may include fluorine, chlorine,bromine, and iodine.

The C₁–C₄ (halo)alkyl group represented by R⁵ or R⁶ may include methyl,ethyl, propyl, 1-methylethyl, 1,1-dimethylethyl, trifluoromethyl,pentafluoroethyl, 3,3,3-trifluoroethyl, and 1,1,2,2-tetrafluoroethoxy.

The C₂–C₄ (halo)alkenyl group represented by R⁵ or R⁶ may include vinyl,1-propenyl, 2-propenyl and 2,2-difluorovinyl.

The C₂–C₄ (halo)alkynyl group represented by R⁵ or R⁶ may includeethynyl, 1-propynyl, 2-propynyl and 3,3,3-trifluoro-1-propynyl.

The C₁–C₄ (halo)alkyloxy group represented by R⁵ or R⁶ may includemethoxy, ethoxy, trifluoromethoxy, bromodifluoromethoxy,difluoromethoxy, chlorodifluoromethoxy, pentafluoroethoxy,2,2,2-trifluoroethoxy, and 1,1,2,2-tetrafluoroethoxy.

The C₁–C₄ (halo)alkylthio group represented by R⁵ or R⁶ may includemethylthio, trifluoromethylthio, 2,2,2-trifluoroethylthio, and1,1,2,2-tetrafluoroethylthio.

The C₁–C₄ (halo)alkylsulfinyl group represented by R⁵ or R⁶ may includemethylsulfinyl and trifluoromethylsulfinyl.

The C₁–C₄ (halo)alkylsulfonyl group represented by R⁵ or R⁶ may includemethylsulfonyl and trifluoromethylsulfonyl.

The C₁–C₄ (halo)alkylcarbonyl group represented by R⁵ or R⁶ may includeacetyl and trifluoroacetyl.

The C₁–C₄ (halo)alkyloxycarbonyl group represented by R⁵ or R⁶ mayinclude methoxycarbonyl and 2,2,2-trifluoroethoxycarbonyl.

The C₁–C₄ (halo)alkylcarbonyloxy group represented by R⁵ or R⁶ mayinclude acetyloxy, propionyloxy, and trifluoroacetyloxy.

The phenyloxy group optionally substituted with halogen or C₁–C₃ alkyl,which is represented by R⁵ or R⁶, may include phenoxy, p-methylphenoxy,m-methylphenoxy, and p-chlorophenoxy.

The phenylthio group optionally substituted with halogen or C₁–C₃ alkyl,which is represented by R⁵ or R⁶, may include phenylthio,p-methylphenylthio, m-methylphenylthio, and p-chlorophenylthio.

The embodiments of the present invention may include the followingcompounds:

The malononitrile compounds of formula (Y) wherein R¹ is hydrogen, andR² is C₁–C₅ (halo)alkyl, C₂–C₅ (halo)alkenyl, or hydrogen;

The malononitrile compounds of formula (Y) wherein R¹ and R² are bothhydrogen;

The malononitrile compounds of formula (Y) wherein R³ is C₁–C₃fluoroalkyl or C₂–C₄ fluoroalkenyl;

The malononitrile compounds of formula (Y) wherein R⁵ is halogen, n isan integer of 0 to 2;

The malononitrile compounds of formula (Y) wherein R⁶ is halogen, cyano,nitro, C₁–C₄ haloalkyl, C₁–C₄ haloalkyloxy, or C₁–C₄ haloalkylthio;

The malononitrile compounds of formula (Y) wherein R⁵ is halogen, n isan integer of 0 to 2, and R⁶ is halogen, cyano, nitro, C₁–C₄ haloalkyl,C₁–C₄ haloalkyloxy, or C₁–C₄ haloalkylthio;

The malononitrile compounds of formula (Y) wherein R³ is C₁–C₃fluoroalkyl or C₂–C₄ fluoroalkenyl, R⁵ is halogen, n is an integer of 0to 2, and R⁶ is halogen, cyano, nitro, C₁–C₄ (halo)alkyl, C₁–C₄(halo)alkyloxy, or C₁–C₄ (halo)alkylthio;

The malononitrile compounds of formula (Y) wherein R¹ and R² are thesame or different and independently C₁–C₃ (halo)alkyl, C₁–C₃(halo)alkyloxy, C₂–C₄ (halo)alkenyl, C₂–C₄ (halo)alkynyl, hydrogen, orcyano; R⁵ and R⁶ are the same or different and independently halogen,cyano, nitro, C₁–C₃ haloalkyl, C₁–C₃ haloalkyloxy, C₁–C₃,(halo)alkylthio, C₁–C₃ (halo)alkylsulfinyl, C₁–C₃ (halo)alkylsulfonyl,C₁–C₃ (halo)alkylcarbonyl, or C₁–C₃ haloalkyloxycarbonyl;

The malononitrile compounds of formula (Y) wherein R¹ is hydrogen, R² isC₁–C₅ (halo)alkyl, C₂–C₅ (halo)alkenyl, or hydrogen, R³ is C₁–C₃fluoroalkyl or C₂–C₄ fluoroalkenyl, R⁵ is halogen, n is an integer of 0to 2, and R⁶ is halogen, cyano, nitro, C₁–C₄ (halo)alkyl, C₁–C₄(halo)alkyloxy, or C₁–C₄ (halo)alkylthio;

The malononitrile compounds of formula (Y) wherein R³ is1,2,2-trifluorovinyl, m is 2, and R⁶ is trifluoromethyl;

The malononitrile compounds of formula (Y) wherein R³ is1,2,2-trifluorovinyl, m is 2, and R⁶ is difluoromethoxy;

The malononitrile compounds of formula (Y) wherein R³ is1,2,2-trifluorovinyl, m is 2, and R⁶ is trifluoromethoxy;

The malononitrile compounds of formula (Y) wherein R³ is1,2,2-trifluorovinyl, m is 2, and R⁶ is trifluoromethylthio;

The malononitrile compounds of formula (Y) wherein R³ is1,2,2-trifluorovinyl, m is 2, and R⁶ is 1,1,2,2-tetrafluoroethoxy;

The malononitrile compounds of formula (Y) wherein R³ is1,2,2-trifluorovinyl, m is 2, and R⁶ is chlorine;

The malononitrile compounds of formula (Y) wherein R³ is1,2,2-trifluorovinyl, m is 2, and R⁶ is bromine;

The malononitrile compounds of formula (Y) wherein R³ is1,2,2-trifluorovinyl, m is 2, and R⁶ is fluorine;

The malononitrile compounds of formula (Y) wherein R³ is1,2,2-trifluorovinyl, m is 2, and R⁶ is cyano;

The malononitrile compounds of formula (Y) wherein R³ is1,2,2-trifluorovinyl, m is 2, and R⁶ is nitro;

The malononitrile compounds of formula (Y) wherein R³ istrifluoromethyl, m is 2, and R⁶ is trifluoromethyl;

The malononitrile compounds of formula (Y) wherein R³ istrifluoromethyl, m is 2, and R⁶ is difluoromethoxy;

The malononitrile compounds of formula (Y) wherein R³ istrifluoromethyl, m is 2, and R⁶ is trifluoromethoxy;

The malononitrile compounds of formula (Y) wherein R³ istrifluoromethyl, m is 2, and R⁶ is trifluoromethylthio;

The malononitrile compounds of formula (Y) wherein R³ istrifluoromethyl, m is 2, and R⁶ is 1,1,2,2-tetrafluoroethoxy;

The malononitrile compounds of formula (Y) wherein R³ istrifluoromethyl, m is 2, and R⁶ is chlorine;

The malononitrile compounds of formula (Y) wherein R³ istrifluoromethyl, m is 2, and R⁶ is bromine;

The malononitrile compounds of formula (Y) wherein R³ istrifluoromethyl, m is 2, and R⁶ is fluorine;

The malononitrile compounds of formula (Y) wherein R³ istrifluoromethyl, m is 2, and R⁶ is cyano;

The malononitrile compounds of formula (Y) wherein R³ istrifluoromethyl, m is 2, and R⁶ is nitro;

The malononitrile compounds of formula (Y) wherein R³ ispentafluoroethyl, m is 2, and R⁶ is trifluoromethyl;

The malononitrile compounds of formula (Y) wherein R³ ispentafluoroethyl, m is 2, and R⁶ is difluoromethoxy;

The malononitrile compounds of formula (Y) wherein R³ ispentafluoroethyl, m is 2, and R⁶ is trifluoromethoxy;

The malononitrile compounds of formula (Y) wherein R³ ispentafluoroethyl, m is 2, and R⁶ is trifluoromethylthio;

The malononitrile compounds of formula (Y) wherein R³ ispentafluoroethyl, m is 2, and R⁶ is 1,1,2,2-tetrafluoroethoxy;

The malononitrile compounds of formula (Y) wherein R³ ispentafluoroethyl, m is 2, and R⁶ is chlorine;

The malononitrile compounds of formula (Y) wherein R³ ispentafluoroethyl, m is 2, and R⁶ is bromine;

The malononitrile compounds of formula (Y) wherein R³ ispentafluoroethyl, m is 2, and R⁶ is fluorine;

The malononitrile compounds of formula (Y) wherein R³ ispentafluoroethyl, m is 2, and R⁶ is cyano;

The malononitrile compounds of formula (Y) wherein R³ ispentafluoroethyl, m is 2, and R⁶ is nitro;

The malononitrile compounds of formula (Y) wherein R³ istrifluoromethyl, m is 1, and R⁶ is trifluoromethyl;

The malononitrile compounds of formula (Y) wherein R³ istrifluoromethyl, m is 1, and R⁶ is trifluoromethoxy;

The malononitrile compounds of formula (Y) wherein R³ istrifluoromethyl, m is 1, and R⁶ is trifluoromethylthio;

The malononitrile compounds of formula (Y) wherein R³ istrifluoromethyl, m is 1, and R⁶ is chlorine;

The malononitrile compounds of formula (Y) wherein R³ istrifluoromethyl, m is 1, and R⁶ is fluorine;

The malononitrile compounds of formula (Y) wherein R³ istrifluoromethyl, m is 1, and R⁶ is cyano;

The malononitrile compounds of formula (Y) wherein R³ istrifluoromethyl, m is 1, and R⁶ is nitro;

The malononitrile compounds of formula (Y) wherein R³ istrifluoromethyl, m is 3, and R⁶ is trifluoromethyl;

The malononitrile compounds of formula (Y) wherein R³ istrifluoromethyl, m is 3, and R⁶ is trifluoromethoxy;

The malononitrile compounds of formula (Y) wherein R³ istrifluoromethyl, m is 3, and R⁶ is trifluoromethylthio;

The malononitrile compounds of formula (Y) wherein R³ istrifluoromethyl, m is 3, and R⁶ is chlorine;

The malononitrile compounds of formula (Y) wherein R³ istrifluoromethyl, m is 3, and R⁶ is fluorine;

The malononitrile compounds of formula (Y) wherein R³ istrifluoromethyl, m is 3, and R⁶ is cyano;

The malononitrile compounds of formula (Y) wherein R³ istrifluoromethyl, m is 3, and R⁶ is nitro;

The malononitrile compounds of formula (Y) wherein R³ is2,2-dichlorovinyl, m is 1, and R⁶ is trifluoromethyl;

The malononitrile compounds of formula (Y) wherein R³ is2,2-dichlorovinyl, m is 1, and R⁶ is trifluoromethoxy;

The malononitrile compounds of formula (Y) wherein R³ is2,2-dichlorovinyl, m is 1, and R⁶ is trifluoromethylthio;

The malononitrile compounds of formula (Y) wherein R³ is2,2-dichlorovinyl, m is 1, and R⁶ is chlorine;

The malononitrile compounds of formula (Y) wherein R³ is2,2-dichlorovinyl, m is 1, and R⁶ is fluorine;

The malononitrile compounds of formula (Y) wherein R³ is2,2-dichlorovinyl, m is 1, and R⁶ is cyano;

The malononitrile compounds of formula (Y) wherein R³ is2,2-dichlorovinyl, m is 1, and R⁶ is nitro;

The malononitrile compounds of formula (Y) wherein R³ is2,2-difluorovinyl, m is 1, and R⁶ is trifluoromethyl;

The malononitrile compounds of formula (Y) wherein R³ is2,2-difluorovinyl, m is 1, and R⁶ is trifluoromethoxy;

The malononitrile compounds of formula (Y) wherein R³ is2,2-difluorovinyl, m is 1, and R⁶ is trifluoromethylthio;

The malononitrile compounds of formula (Y) wherein R³ is2,2-difluorovinyl, m is 1, and R⁶ is chlorine;

The malononitrile compounds of formula (Y) wherein R³ is2,2-difluorovinyl, m is 1, and R⁶ is fluorine;

The malononitrile compounds of formula (Y) wherein R³ is2,2-difluorovinyl, m is 1, and R⁶ is cyano;

The malononitrile compounds of formula (Y) wherein R³ is2,2-difluorovinyl, m is 1, and R⁶ is nitro;

The malononitrile compounds of formula (Y) wherein R³ is3,3,3-trifluoro-1-propenyl, m is 1, and R⁶ is trifluoromethyl;

The malononitrile compounds of formula (Y) wherein R³ is3,3,3-trifluoro-1-propenyl, m is 1, and R⁶ is trifluoromethoxy;

The malononitrile compounds of formula (Y) wherein R³ is3,3,3-trifluoro-1-propenyl, m is 1, and R⁶ is trifluoromethylthio;

The malononitrile compounds of formula (Y) wherein R³ is3,3,3-trifluoro-1-propenyl, m is 1, and R⁶ is chlorine;

The malononitrile compounds of formula (Y) wherein R³ is3,3,3-trifluoro-1-propenyl, m is 1, and R⁶ is fluorine;

The malononitrile compounds of formula (Y) wherein R³ is3,3,3-trifluoro-1-propenyl, m is 1, and R⁶ is cyano;

The malononitrile compounds of formula (Y) wherein R³ is3,3,3-trifluoro-1-propenyl, m is 1, and R⁶ is nitro;

The malononitrile compounds of formula (Y) wherein R³ is3,3,3-trifluoro-1-propynyl, m is 1, and R⁶ is trifluoromethyl;

The malononitrile compounds of formula (Y) wherein R³ is3,3,3-trifluoro-1-propynyl, m is 1, and R⁶ is trifluoromethoxy;

The malononitrile compounds of formula (Y) wherein R³ is3,3,3-trifluoro-1-propynyl, m is 1, and R⁶ is trifluoromethylthio;

The malononitrile compounds of formula (Y) wherein R³ is3,3,3-trifluoro-1-propynyl, m is 1, and R⁶ is chlorine;

The malononitrile compounds of formula (Y) wherein R³ is3,3,3-trifluoro-1-propynyl, m is 1, and R⁶ is fluorine;

The malononitrile compounds of formula (Y) wherein R³ is3,3,3-trifluoro-1-propynyl, m is 1, and R⁶ is cyano;

The malononitrile compounds of formula (Y) wherein R³ is3,3,3-trifluoro-1-propynyl, m is 1, and R⁶ is nitro;

The malononitrile compounds of formula (Y) wherein R³ isheptafluoropropyl, m is 1, and R⁶ is trifluoromethyl;

The malononitrile compounds of formula (Y) wherein R³ isheptafluoropropyl, m is 1, and R⁶ is trifluoromethoxy;

The malononitrile compounds of formula (Y) wherein R³ isheptafluoropropyl, m is 1, and R⁶ is trifluoromethylthio;

The malononitrile compounds of formula (Y) wherein R³ isheptafluoropropyl, m is 1, and R⁶ is chlorine;

The malononitrile compounds of formula (Y) wherein R³ isheptafluoropropyl, m is 1, and R⁶ is fluorine;

The malononitrile compounds of formula (Y) wherein R³ isheptafluoropropyl, m is 1, and R⁶ is cyano;

The malononitrile compounds of formula (Y) wherein R³ isheptafluoropropyl, m is 1, and R⁶ is nitro;

The malononitrile compounds of formula (Y) wherein R³ ispentafluoroethyl, m is 1, and R⁶ is trifluoromethyl;

The malononitrile compounds of formula (Y) wherein R³ ispentafluoroethyl, m is 1, and R⁶ is trifluoromethoxy;

The malononitrile compounds of formula (Y) wherein R³ ispentafluoroethyl, m is 1, and R⁶ is trifluoromethylthio;

The malononitrile compounds of formula (Y) wherein R³ ispentafluoroethyl, m is 1, and R⁶ is chlorine;

The malononitrile compounds of formula (Y) wherein R³ ispentafluoroethyl, m is 1, and R⁶ is fluorine;

The malononitrile compounds of formula (Y) wherein R³ ispentafluoroethyl, m is 1, and R⁶ is cyano;

The malononitrile compounds of formula (Y) wherein R³ ispentafluoroethyl, m is 1, and R⁶ is nitro;

The malononitrile compounds of formula (Y) wherein R³ is fluoromethyl, mis 1, and R⁶ is trifluoromethyl;

The malononitrile compounds of formula (Y) wherein R³ is fluoromethyl, mis 1, and R⁶ is trifluoromethoxy;

The malononitrile compounds of formula (Y) wherein R³ is fluoromethyl, mis 1, and R⁶ is trifluoromethylthio;

The malononitrile compounds of formula (Y) wherein R³ is fluoromethyl, mis 1, and R⁶ is chlorine;

The malononitrile compounds of formula (Y) wherein R³ is fluoromethyl, mis 1, and R⁶ is fluorine;

The malononitrile compounds of formula (Y) wherein R³ is fluoromethyl, mis 1, and R⁶ is cyano;

The malononitrile compounds of formula (Y) wherein R³ is fluoromethyl, mis 1, and R⁶ is nitro;

The malononitrile compounds of formula (Y) wherein R³ is fluoromethyl, mis 2, and R⁶ is trifluoromethyl;

The malononitrile compounds of formula (Y) wherein R³ is fluoromethyl, mis 2, and R⁶ is trifluoromethoxy;

The malononitrile compounds of formula (Y) wherein R³ is fluoromethyl, mis 2, and R⁶ is trifluoromethylthio;

The malononitrile compounds of formula (Y) wherein R³ is fluoromethyl, mis 2, and R⁶ is chlorine;

The malononitrile compounds of formula (Y) wherein R³ is fluoromethyl, mis 2, and R⁶ is fluorine;

The malononitrile compounds of formula (Y) wherein R³ is fluoromethyl, mis 2, and R⁶ is cyano;

The malononitrile compounds of formula (Y) wherein R³ is fluoromethyl, mis 2, and R⁶ is nitro;

The malononitrile compounds of formula (Y) wherein R³ is chloromethyl, mis 1, and R⁶ is trifluoromethyl;

The malononitrile compounds of formula (Y) wherein R³ is chloromethyl, mis 1, and R⁶ is trifluoromethoxy;

The malononitrile compounds of formula (Y) wherein R³ is chloromethyl, mis 1, and R⁶ is trifluoromethylthio;

The malononitrile compounds of formula (Y) wherein R³ is chloromethyl, mis 1, and R⁶ is chlorine;

The malononitrile compounds of formula (Y) wherein R³ is chloromethyl, mis 1, and R⁶ is fluorine;

The malononitrile compounds of formula (Y) wherein R³ is chloromethyl, mis 1, and R⁶ is cyano;

The malononitrile compounds of formula (Y) wherein R³ is chloromethyl, mis 1, and R⁶ is nitro;

The malononitrile compounds of formula (Y) wherein R³ is1,1-difluoroethyl, m is 2, and R⁶ is trifluoromethyl;

The malononitrile compounds of formula (Y) wherein R³ is1,1-difluoroethyl, m is 2, and R⁶ is trifluoromethoxy;

The malononitrile compounds of formula (Y) wherein R³ is1,1-difluoroethyl, m is 2, and R⁶ is trifluoromethylthio;

The malononitrile compounds of formula (Y) wherein R³ is1,1-difluoroethyl, m is 2, and R⁶ is chlorine;

The malononitrile compounds of formula (Y) wherein R³ is1,1-difluoroethyl, m is 2, and R⁶ is fluorine;

The malononitrile compounds of formula (Y) wherein R³ is1,1-difluoroethyl, m is 2, and R⁶ is cyano;

The malononitrile compounds of formula (Y) wherein R³ is1,1-difluoroethyl, m is 2, and R⁶ is nitro;

The malononitrile compounds of formula (Y) wherein R³ is1-(trifluoromethyl)vinyl, m is 1, and R⁶ is trifluoromethyl;

The malononitrile compounds of formula (Y) wherein R³ is1-(trifluoromethyl)vinyl, m is 1, and R⁶ is trifluoromethoxy;

The malononitrile compounds of formula (Y) wherein R³ is1-(trifluoromethyl)vinyl, m is 1, and R⁶ is trifluoromethylthio;

The malononitrile compounds of formula (Y) wherein R³ is1-(trifluoromethyl)vinyl, m is 1, and R⁶ is chlorine;

The malononitrile compounds of formula (Y) wherein R³ is1-(trifluoromethyl)vinyl, m is 1, and R⁶ is fluorine;

The malononitrile compounds of formula (Y) wherein R³ is1-(trifluoromethyl)vinyl, m is 1, and R⁶ is cyano;

The malononitrile compounds of formula (Y) wherein R³ is1-(trifluoromethyl)vinyl, m is 1, and R⁶ is nitro;

The malononitrile compounds of formula (Y) wherein R³ is1-(trifluoromethyl)vinyl, m is 2, and R⁶ is trifluoromethyl;

The malononitrile compounds of formula (Y) wherein R³ is1-(trifluoromethyl)vinyl, m is 2, and R⁶ is trifluoromethoxy;

The malononitrile compounds of formula (Y) wherein R³ is1-(trifluoromethyl)vinyl, m is 2, and R⁶ is trifluoromethylthio;

The malononitrile compounds of formula (Y) wherein R³ is1-(trifluoromethyl)vinyl, m is 2, and R⁶ is chlorine;

The malononitrile compounds of formula (Y) wherein R³ is1-(trifluoromethyl)vinyl, m is 2, and R⁶ is fluorine;

The malononitrile compounds of formula (Y) wherein R³ is1-(trifluoromethyl)vinyl, m is 2, and R⁶ is cyano;

The malononitrile compounds of formula (Y) wherein R³ is1-(trifluoromethyl)vinyl, m is 2, and R⁶ is nitro.

The preferred compounds among the present compounds are the compoundswherein R⁶ is halogen, cyano, nitro, C₁–C₄ haloalkyl, C₁–C₄ haloalkyloxyor C₁–C₄ haloalkylthio; the compounds wherein n is 1 to 3 and at leastone of R⁵ is halogen, cyano, nitro, C₁–C₄ haloalkyl, C₁–C₄ haloalkyloxyor C₁–C₄ (halo)alkylthio; or the compounds wherein R³ is1,2,2-trifluorovinyl, trifluoromethyl, pentafluoroethyl,3,3,3-trifluoro-1-propenyl, heptafluoropropyl, 1,1-difluoroethyl or1-(trifluoromethyl)vinyl. More preferred compounds are the compoundswherein R⁶ is halogen, cyano, nitro, C₁–C₄ fluoroalkyl, C₁–C₄fluoroalkyloxy or C₁–C₄ fluoroalkylthio; the compounds wherein n is 1 to3 and at least one of R⁵ is halogen, cyano, nitro, C₁–C₄ fluoroalkyl,C₁–C₄ fluoroalkyloxy or C₁–C₄ fluoroalkylthio; or the compounds whereinm is 2 and R³ is trifluoromethyl.

The following will describe the production processes for the presentcompounds.

The present compounds can be produced by, for example, the following(Production Process 1) or (Production Process 2).

(Production Process 1)

This is a process by reacting compound (a) with compound (b) in thepresence of a base.

wherein R¹, R², R³, R⁵, R⁶, m, and n are as defined above, and Z ishalogen, methanesulfonyl, trifluoromethanesulfonyl, or toluenesulfonyl.

The reaction is usually carried out in a solvent. The solvent which canbe used in the reaction may include acid amides such asdimethylformamide; ethers such as diethyl ether and tetrahydrofuran;organic sulfur compounds such as dimethylsulfoxide and sulfolane;halogenated hydrocarbons such as 1,2-dichloroethane and chlorobenzene;aromatic hydrocarbons such as toluene and xylene; water; and mixturesthereof

The base which can be used in the reaction may include inorganic basessuch as sodium hydride, sodium hydroxide, potassium hydroxide, andpotassium carbonate; alkali metal alkoxides such as sodium methoxide,sodium ethoxide, and potassium tert-butoxide; alkali metal amides suchas lithium diisopropylamide; and organic bases such as4-dimethylaminopyridine, 1,4-diazabicyclo[2.2.2]octane, and1,8-diazabicylco[5.4.0]-7-undecene. The amount of base used in thereaction is usually in a ratio of 1 to 10 moles relative to 1 mole ofcompound (a).

The reaction temperature is usually in the range of −20° C. to 100° C.

The reaction time is usually in the range of 1 to 24 hours.

The amount of compound (b) used in the reaction is usually in a ratio of1 to 10 moles relative to 1 mole of compound (a).

After the reaction, the reaction mixture is poured into water, followedby ordinary post-treatment procedures including extraction with anorganic solvent and concentration, thereby isolating the desired presentcompounds, which may be purified by a technique such as chromatographyor recrystallization.

(Production Process 2)

This is a process by reacting compound (c) with compound (d) in thepresence of a base.

wherein R¹, R², R³, R⁵, R⁶, m, n, and Z are as defined above.

The reaction is usually carried out in a solvent. The solvent which canbe used in the reaction may include acid amides such asdimethylformamide; ethers such as diethyl ether and tetrahydrofuran;organic sulfur compounds such as dimethylsulfoxide and sulfolane;halogenated hydrocarbons such as 1,2-dichloroethane and chlorobenzene;aromatic hydrocarbons such as toluene and xylene; water; and mixturesthereof

The base which can be used in the reaction may include inorganic basessuch as sodium hydride, sodium hydroxide, potassium hydroxide, andpotassium carbonate; alkali metal alkoxides such as sodium methoxide,sodium ethoxide, and potassium tert-butoxide; alkali metal amides suchas lithium diisopropylamide; and organic bases such as4-dimethylaminopyridine, 1,4-diazabicyclo[2.2.2]octane, and1,8-diazabicylco[5.4.0]-7-undecene. The amount of base used in thereaction is usually in a ratio of 1 to 10 moles relative to 1 mole ofcompound (a).

The reaction temperature is usually in the range of −20° C. to 100° C.

The reaction time is usually in the range of 1 to 24 hours.

The amount of compound (b) used in the reaction is usually in a ratio of1 to 10 moles relative to 1 mole of compound (a).

After the reaction, the reaction mixture is poured into water, followedby ordinary post-treatment procedures including extraction with anorganic solvent and concentration, thereby isolating the desired presentcompounds, which may be purified by a technique such as chromatographyor recrystallization.

The compound (a) can be produced through a route, for example, as shownin the following scheme.

wherein R¹, R², R⁵, R⁶, and n are as defined above.

(Step 1)

The compound (f) can be produced by reacting compound (e) withmalononitrile.

The reaction is usually carried out in a solvent and in the presence ofa base. The solvent which can be used in the reaction may include acidamides such as N,N-dimethylformamide; ethers such as diethyl ether andtetrahydrofuran; halogenated hydrocarbons such as chloroform,1,2-dichloroethane, and chlorobenzene; aromatic hydrocarbons such astoluene and xylene; alcohols such as methanol, ethanol, and isopropanol;and mixtures thereof

The base which can be used in the reaction may includetetrabutylammonium hydroxide. The amount of base used in the reaction isusually in a ratio of 0.01 to 0.5 mole relative to 1 mole of compound(e).

The amount of malononitrile used in the reaction is usually in a ratioof 1 to 10 moles relative to 1 mole of compound (e).

The reaction temperature is usually in the range of −20° C. to 200° C.

The reaction time is usually in the range of 1 to 24 hours.

The reaction may be carried out, while removing, if necessary, waterwhich is generated by the reaction, from the reaction system.

After the reaction, the reaction mixture is poured into water, followedby ordinary post-treatment procedures including extraction with anorganic solvent and concentration, thereby isolating the desired presentcompounds, which may be purified by a technique such as chromatographyor recrystallization.

(Step 2)

(1) The case where R² is a substituent other than hydrogen and cyano:

The compound (a) can be produced by reacting compound (f) with anorganometallic compound.

The reaction is usually carried out in a solvent and, if necessary, inthe presence of a copper salt.

The solvent which can be used in the reaction may include ethers such asdiethyl ether and tetrahydrofuran; aromatic hydrocarbons such as tolueneand xylene; and mixtures thereof

The organometallic compound which can be used in the reaction mayinclude organic magnesium compounds such as methyl magnesium iodide,ethyl magnesium bromide, isopropyl magnesium bromide, vinyl magnesiumbromide, ethynyl magnesium bromide, and dimethyl magnesium; organiclithium compounds such as methyl lithium; organic zinc compounds such asdiethyl zinc; and organic copper compounds such as trifluoromethylcopper. The amount of organometallic compound used in the reaction isusually in a ratio of 1 to 10 moles relative to 1 mole of compound (f).

The copper salt which can be used in the reaction may include copper (I)iodide and copper (I) bromide. The amount of copper salt used in thereaction is usually not greater than 1 mole relative to 1 mole ofcompound (f).

The reaction temperature is usually in the range of −20° C. to 100° C.

The reaction time is usually in the range of 1 to 24 hours.

After the reaction, the reaction mixture is poured into water, followedby ordinary post-treatment procedures including extraction with anorganic solvent and concentration, thereby isolating the desired presentcompounds, which may be purified by a technique such as chromatographyor recrystallization.

(2) The case where R² is hydrogen:

The compound (a) can be produced by subjecting compound (f) toreduction.

The reduction is usually carried out in a solvent.

The solvent which can be used in the reaction may include ethers such asdiethyl ether and tetrahydrofuran; aromatic hydrocarbons such as tolueneand xylene; alcohols such as methanol, ethanol, and propanol; water; andmixtures thereof.

The reducing agent which can be used in the reaction may include sodiumborohydride. The amount of reducing agent used in the reaction isusually in a ratio of 0.25 to 2 moles relative to 1 mole of compound(f).

The reaction time is usually in the range of a moment to 24 hours.

The reaction temperature is usually in the range of 0° C. to 50° C.

After the reaction, the reaction mixture is poured into water, followedby ordinary post-treatment procedures including extraction with anorganic solvent and concentration, thereby isolating the desired presentcompounds, which may be purified by a technique such as chromatographyor recrystallization.

(3) The case where R² is cyano:

The compound (a) can be produced by reacting compound (f) with acyanide.

The solvent which can be used in the reaction may include ethers such asdiethyl ether and tetrahydrofuran; aromatic hydrocarbons such as tolueneand xylene; and mixtures thereof.

The cyanide which can be used in the reaction may includetetrabutylammonium cyanide. The amount of cyanide used in the reactionis usually in a ratio of 1 to 10 moles relative to 1 mole of compound(f).

The reaction temperature is usually in the range of −20° C. to 100° C.

The reaction time is usually in the range of 1 to 24 hours.

After the reaction, the reaction mixture is poured into water, followedby ordinary post-treatment procedures including extraction with anorganic solvent and concentration, thereby isolating the desired presentcompounds, which may be purified by a technique such as chromatographyor recrystallization.

The pests against which the present compounds exhibit controllingactivity may include insect pests, acarine pests, and nematode pests,specific examples which are as follows:

Hemiptera:

Delphacidae such as Laodelphax striatellus, Nilaparvata lugens, andSogatella furcifera;

Deltocephalidae such as Nephotettix cincticeps and Nephotettixvirescens;

Aphididae such as Aphis gossypii and Myzus persicae;

Pentatomidae such as Nezara antennata, Riptortus clavetus Eysarcorislewisi, Eysarcoris parvus, Plautia stali and Halyomorpha misia;

Aleyrodidae such as Trialeurodes vaporariorum and Bemisia argentifolii;

Coccidae such as Aonidiella aurantii, Comstockaspis perniciosa, Unaspiscitri, Ceroplastes rubens, and Icerya purchasi;

Tingidae;

Psyllidae;

Lepidoptera:

Pyralidae such as Chilo suppressalis, Cnaphalocrocis medinalis, Notarchaderogata, and Plodia interpunctella;

Noctuidae such as Spodoptera litura, Pseudaletia separata, Thoricoplusiaspp., Heliothis spp., and Helicoverpa spp.;

Pieridae such as Pieris rapae;

Tortricidae such as Adoxophyes spp., Grapholita molesta, and Cydiapomonella;

Carposinidae such as Carposina niponensis;

Lyonetiidae such as Lyonetia spp.;

Lymantriidae such as Lyamantria spp. and Euproctis spp.;

Yponomentidae such as Plutella xylostella;

Gelechiidae such as Pectinophora gossypiella;

Arctiidae such as Hyphantria cunea;

Tineidae such as Tinea translucens and Tineola bisselliella;

Diptera:

Calicidae such as Culex pipiens pallens, Culex tritaeniorhynchus, andCulex quinquefasciatus;

Aedes spp. such as Aedes aegypti and Aedes albopictus,

Anopheles spp. such as Anopheles sinensis;

Chironomidae;

Muscidae such as Musca domestica and Muscina stabulans;

Calliphoridae;

Sarcophagidae;

Fanniidae;

Anthomyiidae such as Delia platura and Delia antiqua;

Tephritidae;

Drosophilidae;

Psychodidae;

Simuliidae;

Tabanidae;

Stomoxyidae;

Agromyzidae;

Coleoptera:

Diabrotica spp. such as Diabrotica virgifera and Diabroticaundecimpunctata howardi;

Scarabaeidae such as Anomala cuprea and Anomala rufocuprea;

Curculionidae such as Sitophilus zeamais, Lissorhoptrus oryzophilus, andCallosohruchuys chienensis;

Tenebrionidae such as Tenebrio molitor and Tribolium castaneum;

Chrysomelidae such as Oulema oryzae, Aulacophora femoralis, Phyllotretastriolata, and Leptinotarsa decemlineata;

Anobiidae;

Epilachna spp. such as Epilachna vigintioctopunctata;

Lyctidae;

Bostrychidae;

Cerambycidae;

Paederus fuscipes;

Dictyoptera:

Blattella germanica, Periplaneta fuliginosa, Periplaneta americana,Periplaneta brunnea, and Blatta orientalis;

Thysanoptera:

Thrips palmi, Thrips tabaci, Frankliniella occidentalis, Frankliniellaintonsa;

Hymenoptera:

Formicidae;

Vespidae;

Bethylidae;

Tenthredinidae such as Athalia japonica;

Orthoptera:

Gryllotalpidae;

Acrididae;

Siphonaptera:

Ctenocephalides felis, Ctenocephalides canis, Pulex irritans, Xenopsyllacheopis;

Anoplura:

Pediculus humanus corporis, Phthirus pubis, Haematopinus eurysternus,and Dalmalinia ovis;

Isoptera:

Reticulitermes speratus and Coptotermes formosanus;

Acarina:

Tetranychidae such as Tetranychus urticae, Tetranychus kanzawai,Panonychus citri, Panonychus ulmi, and Oligonychus spp.;

Eriophyidae such as Aculops pelekassi and Aculus schlechtendali;

Tarsonemidae such as Polyphagotarsonemus latus;

Tenuipalpidae;

Tuckerellidae;

Ixodidae such as Haemaphysalis longicornis, Haemaphysalis flava,Dermacentor taiwanicus, Ixodes ovatus, Ixodes persulcatus, and Boophilusmicroplus;

Acaridae such as Tyrophagus putrescentiae;

Epidermoptidae such as Dermatophagoides farinae and Dermatophagoidesptrenyssnus;

Cheyletidae such as Cheyletus eruditus, Cheyletus malaccensis, andCheyletus moorei;

Dermanyssidae;

Arachnida:

Chiracanthium japonicum and Latrodectus hasseltii;

Chilopoda:

Thereuonema hilgendorfi and Scolopendra subspinipes;

Diplopoda:

Oxidus gracilis and Nedyopus tambanus;

Isopoda:

Armadillidium vulgare;

Gastropoda:

Limax marginatus and Limax flavus;

Nematoda:

Pratylenchus coffeae, Pratylenchus fallax, Heterodera glycines,Globodera rostochiensis, Meloidogyne hapla, and Meloidogyne incognita.

When the present compounds are used as the active ingredients ofpesticide compositions, they may be used as such without addition of anyother ingredients. However, they are usually used in admixture withsolid carriers, liquid carriers and/or gaseous carriers, and ifnecessary, by addition of adjuvants such as surfactants, followed byformulation into various forms such emulsifiable concentrates, oilformulations, flowables, dusts, wettable powders, granules, pasteformulations, microcapsule formulations, foams, aerosol formulations,carbon dioxide gas formulations, tablets, or resin formulations. Theseformulations may be used by processing into poison baits, shampoo,mosquito coils, electric mosquito mats, smokes, fumigants, or sheets.

In these formulations, the present compounds are usually contained eachin an amount of 0.1% to 95% by weight.

The solid carrier which can be used in the formulation may include thefollowing materials in fine powder or granular form: clays (e.g., kaolinclay, diatomaceous earth, bentonite, Fubasami clay, acid clay); talc,ceramic, and other inorganic minerals (e.g., sericite, quartz, sulfur,activated carbon, calcium carbonate, hydrated silica); and chemicalfertilizers (e.g., ammonium sulfate, ammonium phosphate, ammoniumnitrate, ammonium chloride, urea).

The liquid carrier may include aromatic or aliphatic hydrocarbons (e.g.,xylene, toluene, alkylnaphthalene, phenylxylylethane, kerosine, lightoils, hexane, cyclohexane); halogenated hydrocarbons (e.g.,chlorobenzene, dichloromethane, dichloroethane, trichloroethane);alcohols (e.g., methanol, ethanol, isopropyl alcohol, butanol, hexanol,ethylene glycol); ethers (e.g., diethyl ether, ethylene glycol dimethylether, diethylene glycol monomethyl ether, diethylene glycol monoethylether, propylene glycol monomethyl ether, tetrahydrofuran, dioxane);esters (e.g., ethyl acetate, butyl acetate); ketones (e.g., acetone,methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone); nitriles(acetonitrile, isobutyronitrile); sulfoxides (e.g., dimethylsulfoxide);acid amides (e.g., N,N-dimethylformamide, N,N-dimethylacetamide);vegetable oils (e.g., soy bean oil and cotton seed oil); plant essentialoils (e.g., orange oil, hyssop oil, lemon oil); and water.

The gaseous carrier may include butane gas, Freon gas, liquefiedpetroleum gas (LPG), dimethyl ether, and carbon dioxide.

The surfactant may include alkyl sulfate salts; alkylsulfonic acidsalts; alkylarylsulfonic acid salts; alkyl aryl ethers and theirpolyoxyethylene derivatives; polyethylene glycol ethers; polyol esters;and sugar alcohol derivatives.

The other adjuvants may include binders, dispersants, and stabilizers,specific examples of which are casein, gelatin, polysaccharides (e.g.,starch, gum arabic, cellulose derivatives, alginic acid), ligninderivatives, bentonite, sugars, synthetic water-soluble polymers (e.g.,polyvinyl alcohol, polyvinylpyrrolidone, polyacrylic acid), PAP(isopropyl acid phosphate), BHT (2,6-di-t-butyl-4-methylphenol), BHA(mixtures of 2-t-butyl-4-methoxyphenol and 3-t-butyl-4-methoxyphenol),vegetable oils, mineral oils, fatty acids, and fatty acid esters.

The base material for resin formulations may include vinyl chloridepolymers and polyurethanes. These base materials may contain, ifnecessary, plasticizers such as phthalic acid esters (e.g., dimethylphthalate, dioctyl phthalate), adipic acid esters, and stearic acid. Theresin formulations can be obtained by kneading the present compoundsinto the base materials with an ordinary kneader and subsequent formingsuch as injection molding, extrusion, or pressing. They can beprocessed, if necessary, though further forming and cutting into resinformulations in various shapes such as plates, films, tapes, nets, orstrings. These resin formulations are processed as, for example, collarsfor animals, ear tags for animals, sheet formulations, attractivestrings, or poles for horticultural use.

The base material for poison baits may include grain powders, vegetableoils, sugars, and crystalline cellulose. If necessary, additional agentsmay be added, including antioxidants such as dibutylhydroxytoluene andnordihydroguaiaretic acid; preservatives such as dehydroacetic acid;agents for preventing children and pets from erroneously eating, such ashot pepper powder; and pest-attractive flavors such as cheese flavor,onion flavor, and peanut oil.

The pesticide compositions of the present invention may be used by, forexample, direct application to pests and/or application to the habitatsof pests (e.g., plant bodies, animal bodies, soil).

When the pesticide compositions of the present invention are used forthe control of pests in agriculture and forestry, their applicationamounts are usually 1 to 10,000 g/ha, preferably 10 to 500 g/ha.Formulations such as emulsifiable concentrates, wettable powders,flowables, and microcapsule formulations are usually used after dilutionwith water to have an active ingredient concentration of 1 to 1000 ppm,while formulations such as dusts and granules are usually used as such.These formulations may be directly applied to plants to be protectedfrom pests. These formulations can also be incorporated into soil forthe control of pests inhabiting the soil, or can also be applied to bedsbefore planting or applied to planting holes or plant bottoms in theplanting. Further, the pesticide compositions of the present inventionin the form of sheet formulations can be applied by the methods in whichthe sheet formulations are wound around plants, disposed in the vicinityof plants, or laid on the soil surface at the plant bottoms.

When the pesticide compositions of the present invention are used forthe prevention of epidemics, their application amounts as activeingredient amounts are usually 0.001 to 10 mg/m³ for spatial applicationor 0.001 to 100 mg/m² for planar application. Formulations such asemulsifiable concentrates, wettable powders, and flowables are usuallyapplied after dilution with water to have an active ingredientconcentration of 0.01 to 10,000 ppm, while formulations such as oilformulations, aerosols, smokes, or poison baits are usually applied assuch.

When the pesticide compositions of the present invention are used forthe control of external parasites on domestic animals such as cattle,sheep, goat, and fowl or small animals such as dogs, cats, rats, andmice, they can be used by the veterinarily well-known methods. As thespecific methods of use, administration is achieved by, for example,tablets, feed incorporation, suppositories, or injections (e.g.,intramuscular, subcutaneous, intravenous, intraperitoneal) for systemiccontrol, or by, for example, spraying, pour-on treatment, or spot-ontreatment with an oil formulation or an aqueous solution, washinganimals with a shampoo formulation, or attachment of a collar or ear tagprepared from a resin formulation to animals for non-systemic control.The amounts of the present compounds when administered to animal bodiesare usually in the range of 0.1 to 1000 mg per 1 kg weight of eachanimal.

The pesticide compositions of the present invention can also be used inadmixture or combination with other insecticides, nematocides,acaricides, bactericides, fungicides, herbicides, plant growthregulators, synergists, fertilizers, soil conditioners, animal feeds,and the like.

Examples of the insecticides and acaricides include organophosphoruscompounds such as fenitrothion[O,O-dimethylO-(3-methyl-4-nitrophenyl)phosphorothioate], fenthion[O,O-dimethylO-(3-methyl-4-(methylthio)phenyl)phosphorothioate], diazinon[O,O-diethylO-2-isopropyl-6-methylpyrimidin-4-yl phosphorothioate],chlorpyrifos[O,O-diethyl O-3,5,6-trichloro-2-pyridyl phosphorothioate],DDVP[2,2-dichlorovinyl dimethyl phosphate], cyanophos[O-4-cyanophenylO,O-dimethyl phosphorothioate], dimethoate[O,O-dimethylS-(N-methylcarbamoylmethyl)dithiophosphate], phenthoate[ethyl2-dimethoxyphosphinothioylthio(phenyl)acetate],malathion[diethyl(dimethoxyphosphinothioylthio)succinate], andazinphosmethyl[S-3,4-dihydro-4-oxo-1,2,3-benzotriazin-3-ylmethylO,O-dimethyl phosphorodithioate]; carbamate compounds such asBPMC(2-sec-butylphenyl methylcarbamate), benfracarb[ethylN-[2,3-dihydro-2,2-dimethylbenzofuran-7-yloxycarbonyl(methyl)aminothio]-N-isopropyl-β-alaninate],propoxur[2-isopropoxyphenyl N-methylcarbamate] and carbaryl[1-naphthylN-methylcarbamate]; pyrethroid compounds such asetofenprox[2-(4-ethoxyphenyl)-2-methylpropyl 3-phenoxybenzyl ether],fenvalerate[(RS)-α-cyano-3-phenoxybenzyl(RS)-2-(4-chlorophenyl)-3-methyl-butyrate],esfenvalerate[(S)-α-cyano-3-phenoxybenzyl(S)-2-(4-chlorophenyl)-3-methyl-butyrate],fenpropathrin[(RS)-α-cyano-3-phenoxybenzyl2,2,3,3-tetramethylcyclopropanecarboxylate],cypermethrin[(RS)-α-cyano-3-phenoxybenzyl(1RS)-cis,trans-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate],permethrin[3-phenoxybenzyl(1RS)-cis,trans-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate],cyhalothrin[(RS)-α-cyano-3-phenoxybenzyl(Z)-(1RS)-cis-3-(2-chloro-3,3,3-trifluoroprop-1-enyl)-2,2-dimethylcyclopropanecarboxylate],deltamethrin[(S)-α-cyano-3-phenoxybenzyl(1R)-cis-3-(2,2-dibromovinyl)-2,2-dimethylcyclopropane-carboxylate],cycloprothrin[(RS)-α-cyano-3-phenoxybenzyl(RS)-2,2-dichloro-1-(4-ethoxyphenyl)cyclopropanecarboxylate],fluvalinate[α-cyano-3-phenoxybenzylN-(2-chloro-α,α,α-trifluoro-p-tolyl)-D-valinate],bifenthrin[2-methylbiphenyl-3-ylmethyl(Z)-(1RS)-cis-3-(2-chloro-3,3,3-trifluoroprop-1-enyl)-2,2-dimethylcyclopropanecarboxylate],2-methyl-2-(4-bromodifluoro-methoxyphenyl)propyl 3-phenoxybenzyl ether,tralomethrin[(S)-α-cyano-3-phenoxybenzyl(1R)-cis)-3-{(1RS)(1,2,2,2-tetrabromoethyl)}-2,2-dimethyl-cyclopropanecarboxylate],silafluofen[(4-ethoxyphenyl){3-(4-fluoro-3-phenoxyphenyl)propyl}-dimethylsilane],d-phenothrin-[3-phenoxybenzyl(1R)-cis,trans)-chrysanthemate],cyphenothrin[(RS)-α-cyano-3-phenoxybenzyl(1R)-cis,trans)-chrysanthemate],d-resmethrin[5-benzyl-3-furylmethyl(1R)-cis,trans)-chrysanthemate],acrinathrin[(S)-α-cyano-3-phenoxybenzyl(1R,cis(Z))-2,2-dimethyl-3-{3-oxo-3-(1,1,1,3,3,3-hexafluoropropyloxy)propenyl}cyclopropanecarboxylate],cyfluthrin[(RS)-α-cyano-4-fluoro-3-phenoxybenzyl3-(2,2-dichlorovinyl)-2,2-dimethylcydopropanecarboxylate],tefluthrin[2,3,5,6-tetrafluoro-4-methylbenzyl(1RS-cis(Z))-3-(2-chloro-3,3,3-trifluoroprop-1-enyl)-2,2-dimethylcyclopropanecarboxylate],transfluthrin[2,3,5,6-tetrafluorobenzyl(1R)-trans)-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate],tetramethrin[3,4,5,6-tetrahydrophthalimidomethyl(1RS)-cis,trans-chrysanthemate],allethrin[(RS)-3-allyl-2-methyl-4-oxocyclopent-2-enyl(1RS)-cis,trans-chrysanthemate],prallethrin[(S)-2-methyl-4-oxo-3-(2-propynyl)cyclopent-2-enyl(1R)-cis,trans-chrysanthemate],empenthrin[(RS)-1-ethynyl-2-methyl-2-pentenyl(1R)-cis,trans-chrysanthemate],imiprothrin[2,5-dioxo-3-(prop-2-ynyl)imidazolidin-1-ylmethyl(1R)-cis,trans-2,2-dimethyl-3-(2-methylprop-1-enyl)cyclopropanecarboxylate],d-furamethrin[5-(2-propynyl)furfuryl(1R)-cis,trans-chrysanthemate] and5-(2-propynyl)furfuryl 2,2,3,3-tetramethylcyclopropanecarboxylate;neonicotinoid derivatives such asN-cyano-N′-methyl-N′-(6-chloro-3-pyridylmethyl)acetamidine;nitenpyram[N-(6-chloro-3-pyridylmethyl)-N-ethyl-N′-methyl-2-nitrovynylidenediamine];thiacloprid[1-(2-chloro-5-pyridylmethyl)-2-cyanoiminothiazoline];thiamethoxam[3-((2-chloro-5-thiazolyl)methyl)-5-methyl-4-nitroiminotetrahydro-1,3,5-oxadiazine],1-methyl-2-nitro-3-((3-tetrahydrofuryl)methyl)guanidine and1-(2-chloro-5-thiazolyl)methyl-3-methyl-2-nitroguanidine;nitroiminohexahydro-1,3,5-triazine derivatives; chlorinated hydrocarbonssuch asendosulfan[6,7,8,9,10,10-hexachloro-1,5,5a,6,9,9α-hexahydro-6,9-methano-2,4,3-benzodioxathiepineoxide], γ-BHC[1,2,3,4,5,6-hexachlorocyclohexane] and1,1-bis(chlorophenyl)-2,2,2-trichloroethanol; benzoylphenylureacompounds such aschlorfluazuron[1-(3,5-dichloro-4-(3-chloro-5-trifluoromethylpyridyn-2-yloxy)phenyl)-3-(2,6-difluorobenzoyl)urea],teflubenzuron[1-(3,5-dichloro-2,4-difluorophenyl)-3-(2,6-difluorobenzoyl)urea]andflufenoxuron[1-(4-(2-chloro-4-trifluoromethylphenoxy)-2-fluorophenyl)-3-(2,6-difluorobenzoyl)urea];juvenile hormone like compounds such as pyriproxyfen[4-phenoxyphenyl2-(2-pyridyloxy)propyl ether], methoprene[isopropyl(2E,4E)-11-methoxy-3,7,11-trimethyl-2,4-dodecadienoate] andhydroprene[ethyl(2E,4E)-11-methoxy-3,7,11-trimethyl-2,4-dodecadienoate];thiourea derivatives such asdiafenthiuron[N-(2,6-diisopropyl-4-phenoxyphenyl)-N′-tert-butylcarbodiimide];phenylpyrazole compounds;4-bromo-2-(4-chlorophenyl)-1-ethoxymethyl-5-trifluoromethylpyrrol-3-carbonitrile[chlorfenapil];metoxadiazone[5-methoxy-3-(2-methoxyphenyl)-1,3,4-oxadiazol-2(3H)-one],bromopropylate[isopropyl 4,4′-dibromobenzilate],tetradifon[4-chlorophenyl 2,4,5-trichlorophenyl sulfone],chinomethionat[S,S-6-methylquinoxaline-2,3-diyldithiocarbonate],pyridaben[2-tert-butyl-5-(4-tertbutylbenzylthio)-4-chloropyridazin-3(2H)-one],fenpyroximate[tert-butyl(E)-4-[(1,3-dimethyl-5-phenoxypyrazol-4-yl)methyleneaminooxymethyl]benzoate],tebufenpyrad[N-(4-tert-butylbenzyl)-4-chloro-3-ethyl-1-methyl-5-pyrazolecarboxamide],polynactins complex [tetranactin, dinactin and trinactin],pyrimidifen[5-chloro-N-[2-{4-(2-ethoxyethyl)-2,3-dimethylphenoxy}ethyl]-6-ethylpyrimidin-4-amine],milbemectin, abamectin, ivermectin and azadirachtin[AZAD]. Examples ofthe synergists include bis-(2,3,3,3-tetrachloropropyl)ether(S-421),N-(2-ethylhexyl)bicyclo[2.2.1]hept-5-ene-2,3-dicarboximide (MGK-264) andα-[2-(2-butoxyethoxy)ethoxy]-4,5-methylenedioxy-2-propyltoluene(piperonyl butoxide).

The present invention will further be illustrated by the followingproduction examples, formulation examples, and test examples; however,the present invention is not limited only to these examples. In theformulation examples, the present compound numbers are those shown inTable 1 below.

The following will describe some production examples for the presentcompounds.

PRODUCTION EXAMPLE 1

First, 0.50 g of (4-chlorobenzyl)malononitrile was dissolved in 10 ml ofN,N-dimethylformamide, to which 0.16 g of sodium hydride (60% in oil)was added under ice cooling. After the evolution of hydrogen gas ceased,while stirring under ice cooling, 0.48 ml of 2,3-dichloropropene wasadded dropwise, followed by stirring at room temperature for 5 hours.Then, 10% hydrochloric acid was added to the reaction mixture, which wasextracted with diethyl ether. The organic layer was successively washedwith 10% hydrochloric acid, a saturated aqueous sodium chloridesolution, dried over anhydrous magnesium sulfate, and then concentratedunder reduced pressure. The residue was subjected to silica gel columnchromatography to give 0.19 g of2-(4-chlorobenzyl)-2-(2-chloro-2-propenyl)malononitrile (the presentcompound (1)).

Yield: 27%;

m.p.: 85.5° C.

PRODUCTION EXAMPLE 2

Using 0.50 g of (4-(trifluoromethylthio)benzyl)malononitrile, 5 ml ofN,N-dimethylformamide, 90 mg of sodium hydride (60% in oil), and 0.26 gof 2,3-dichloropropene, and according to the process described in theProduction Example 1, there was obtained 0.30 g of2-(2-chloro-2-propenyl)-2-(4-(trifluoromethylthio)benzyl)malononitrile(the present compound (2)).

Yield: 47%;

¹H-NMR (CDCl₃, TMS, δ (ppm)): 3.05 (2H, s), 3.32 (2H, s), 5.58–5.66 (2H,m), 7.48 (2H, d), 7.73 (2H, d).

PRODUCTION EXAMPLE 3

Using 0.1 g of benzylmalononitrile, 5 ml of N,N-dimethylformamide, 0.073g of cesium carbonate, and 0.1 g of 2,2,2-trifluoroethyltrifluoromethanesulfonate, and according to the process described in theProduction Example 1, there was obtained 0.057 g of2-benzyl-2-(2,2,2-trifluoroethyl)malononitrile (the present compound(3)).

Yield: 40%;

¹H-NMR (CDCl₃, TMS, δ (ppm)): 2.76 (2H, q), 3.36 (2H, s), 7.37–7.47 (5H,m).

PRODUCTION EXAMPLE 4

Using 0.1 g of benzylmalononitrile, 5 ml of N,N-dimethylformamide, 0.010g of sodium hydride (60% in oil), and 0.04 g of4-bromo-1,1,2-trifluoro-1-butene, and according to the process describedin the Production Example 1, there was obtained 0.042 g of2-benzyl-2-(3,4,4-trifluoro-3-butenyl)malononitrile (the presentcompound (4)).

Yield: 57%;

¹H-NMR (CDCl₃, TMS, δ (ppm)): 2.17–2.23 (2H, m), 2.64–2.78 (2H, m), 3.27(2H, s), 7.34–7.45 (5H, m).

PRODUCTION EXAMPLE 5

Using 0.3 g of (4-(trifluoromethoxy)benzyl)malononitrile, 5 ml ofN,N-dimethylformamide, 0.073 g of cesium carbonate, and 0.35 g of2,2,3,3,3-pentafluoropropyl trifluoromethanesulfonate, and according tothe process described in the Production Example 1, there was obtained0.12 g of2-(2,2,3,3,3-pentafluoropropyl)-2-(4-(trifluoromethoxy)benzyl)malononitrile(the present compound (5)).

Yield: 29%;

¹H-NMR (CDCl₃, TMS, δ (ppm)): 2.76 (2H, t), 3.38 (2H, s), 7.30 (2H, d),7.46 (2H, d)

PRODUCTION EXAMPLE 6

Using 0.3 g of (3,3,3-trifluoropropyl)malononitrile, 3 ml ofN,N-dimethylformamide, 0.08 g of sodium hydride (60% in oil), and 0.4 gof 4-acetylbenzyl bromide, and according to the process described in theProduction Example 1, there was obtained 0.43 g of2-(4-acetylbenzyl)-2-(3,3,3-trifluoropropyl)malononitrile (the presentcompound (6)).

Yield: 78%;

¹H-NMR (CDCl₃, TMS, δ (ppm)): 2.22–2.34 (2H, m), 2.51–2.61 (2H, m), 2.67(3H, s), 3.42 (2H, s), 7.50 (2H, d), 7.97 (2H, d).

PRODUCTION EXAMPLE 7

Using 0.30 g of (2,6-dichloro-4-(trifluoromethyl)benzyl)malononitrile, 5ml of N,N-dimethylformamide, 0.05 g of sodium hydride (60% in oil), and0.20 g of 1-bromo-3,3,3-trifluoropropane, and according to the processdescribed in the Production Example 1, there was obtained 0.21 g of2-(2,6-dichloro-4-(trifluoromethyl)benzyl)-2-(3,3,3-trifluoropropyl)malononitrile(the present compound (7)).

Yield: 53%;

¹H-NMR (CDCl₃, TMS, δ (ppm)): 2.41–2.49 (2H, m), 2.52–2.63 (2H, m), 3.79(2H, s), 7.68 (2H, s).

PRODUCTION EXAMPLE 8

Using 0.30 g of (4-(trifluoromethyl)benzyl)malononitrile, 6 ml ofN,N-dimethylformamide, 0.60 g of sodium hydride (60% in oil), and 0.38 gof 4-iodo-1,1,1,2,2-pentafluorobutane, and according to the processdescribed in the Production Example 1, there was obtained 0.30 g of2-(3,3,4,4,4-pentafluorobutyl)-2-(4-(trifluoromethyl)benzyl)malononitrile(the present compound (8)).

Yield: 54%;

¹H-NMR (CDCl₃, TMS, Δ (ppm)): 2.27–2.62 (4H, m), 3.86 (2H, s), 7.53 (2H,d), 7.71 (2H, d).

And there was obtained 15 mg of2-(3,4,4,4-tetrafluoro-2-butenyl)-2-(4-(trifluoromethyl)benzyl)malononitrile(the present compound (48)) as low-polar compound.

Yield: 3%;

¹H-NMR (CDCl₃, TMS, δ (ppm)): 2.96 (2H, d), 3.30 (2H, s), 5.78 (1H, dt),7.53 (2H, d), 7.71 (2H, d).

PRODUCTION EXAMPLE 9

Using 3.86 g of (4-bromobenzyl)malononitrile, 25 ml ofN,N-dimethylformamide, 0.72 g of sodium hydride (60% in oil), and 3.20 gof 1-bromo-3,3,3-trifluoropropane, and according to the processdescribed in the Production Example 1, there was obtained 4.61 g of2-(4-bromobenzyl)-2-(3,3,3-trifluoropropyl)malononitrile (the presentcompound (9)).

Yield: 85%;

¹H-NMR (CDCl₃, TMS, δ (ppm)): 2.18–2.27 (2H, m), 2.45–2.60 (2H, m), 3.22(2H, s), 7.26 (2H, d), 7.57 (2H, d).

PRODUCTION EXAMPLE 10

Using 0.30 g of (4-(trifluoromethoxy)benzyl)malononitrile, 10 ml ofN,N-dimethylformamide, 0.06 g of sodium hydride (60% in oil), and 0.38 gof 4-iodo-1,1,1,2,2-pentafluorobutane, and according to the processdescribed in the Production Example 1, there was obtained 0.15 g of2-(3,3,4,4,4-pentafluorobutyl)-2-(4-(trifluoromethoxy)benzyl)malononitrile(the present compound (10)).

Yield: 28%;

¹H-NMR (CDCl₃, TMS, δ (ppm)): 2.21–2.62 (4H, m), 3.30 (2H, s), 7.27 (2H,d), 7.43 (2H, d).

PRODUCTION EXAMPLE 11

Under nitrogen atmosphere, 0.40 g of2-(2-formylethyl)-2-(4-(trifluoromethyl)benzyl)malononitrile wasdissolved in 10 ml of trichlorofluoromethane, to which 0.20 ml ofdiethylaminosulfur trifluoride was added dropwise slowly, and thenstirred for 30 minutes. Then, water was added to the reaction mixture,which was extracted with ethyl acetate. The organic layer was washedwith a saturated aqueous sodium chloride solution, dried over anhydrousmagnesium sulfate, and then concentrated under reduced pressure. Theresidue was subjected to silica gel column chromatography to give 0.15 gof 2-(3,3-difluoropropyl)-2-(4-(trifluoromethyl)benzyl)malononitrile(the present compound (11)).

Yield: 34%;

¹H-NMR (CDCl₃, TMS, δ (ppm)): 2.19–2.34 (4H, m), 3.31 (2H, s), 6.00 (1H,tt), 7.53 (2H, d), 7.71 (2H,d).

PRODUCTION EXAMPLE 12

Using 0.50 g of benzylmalononitrile, 10 ml of N,N-dimethylformamide,0.14 g of sodium hydride (60% in oil), and 0.63 g of1-bromo-3,3,3-trifluoropropane, and according to the process describedin the Production Example 1, there was obtained 0.14 g of2-benzyl-2-(3,3,3-trifluoropropyl)malononitrile (the present compound(12)).

Yield: 17%;

¹H-NMR (CDCl₃, TMS, δ (ppm)): 2.20–2.27 (2H, m), 2.45–2.59 (2H, m), 3.28(2H, s), 7.34–7.48 (5H, m).

PRODUCTION EXAMPLE 13

Using 0.50 g of (4-(trifluoromethylthio)benzyl)malononitrile, 10 ml ofN,N-dimethylformamide, 0.09 g of sodium hydride (60% in oil), and 0.38 gof 1-bromo-3,3,3-trifluoropropane, and according to the processdescribed in the Production Example 1, there was obtained 0.03 g of2-(4-(trifluoromethylthio)benzyl)-2-(3,3,3-trifluoropropyl)malononitrile(the present compound (13)).

Yield: 11%;

¹H-NMR (CDCl₃, TMS, δ (ppm)): 2.20–2.29 (2H, m), 2.51–2.62 (2H, m), 3.29(2H, s), 7.45 (2H, d), 7.73 (2H, d).

PRODUCTION EXAMPLE 14

Using 0.80 g of2-(3-hydroxypropyl)-2-(4-(trifluoromethyl)benzyl)-malononitrile, 8 ml ofdichloromethane and 0.3 ml of Diethylaminosulfur trifluoride, andaccording to the process described in the Production Example 11, therewas obtained 0.05 g of2-(3-fluoropropyl)-2-(4-(trifluoromethyl)benzyl)malononitrile (thepresent compound (14)).

Yield: 5%;

¹H-NMR (CDCl₃, TMS, δ (ppm)): 2.14–2.20 (4H, m), 3.30 (2H, s), 4.59 (2H,dt), 7.53 (2H, d), 7.69 (2H, d).

PRODUCTION EXAMPLE 15

Using 1.00 g of (4-chlorobenzyl)malononitrile, 10 ml ofN,N-di-methylformamide, 1.0 g of sodium hydride (60% in oil), and 0.93 gof 1-bromo-3,3,3-trifluoropropane, and according to the processdescribed in the Production Example 1, there was obtained 0.21 g of2-(4-chlorobenzyl)-2-(3,3,3-trifluoropropyl)malononitrile (the presentcompound (15)).

Yield: 22%;

¹H-NMR (CDCl₃, TMS, δ (ppm)): 2.17–2.26 (2H, m), 2.48–2.63 (2H, m), 3.24(2H, s), 7.32 (2H, d), 7.42 (2H, d).

PRODUCTION EXAMPLE 16

Using 1.00 g of (4-fluorobenzyl)malononitrile, 15 ml ofN,N-di-methylformamide, 0.23 g of sodium hydride (60% in oil), and 1.02g of 1-bromo-3,3,3-trifluoropropane, and according to the processdescribed in the Production Example 1, there was obtained 0.34 g of2-(4-fluorobenzyl)-2-(3,3,3-trifluoropropyl)malononitrile (the presentcompound (16)).

Yield: 22%;

¹H-NMR (CDCl₃, TMS, δ (ppm)): 2.20–2.27 (2H, m), 2.47–2.62 (2H, m), 3.24(2H, s), 7.13 (2H, dd), 7.37 (2H, dd).

PRODUCTION EXAMPLE 17

Using 0.50 g of (2,4,6-trifluorobenzyl)malononitrile, 10 ml ofN,N-di-methylformamide, 0.11 g of sodium hydride (60% in oil), and 0.46g of 1-bromo-3,3,3-trifluoropropane, and according to the processdescribed in the Production Example 1, there was obtained 0.07 g of2-(2,4,6-trifluorobenzyl)-2-(3,3,3-trifluoropropyl)malononitrile (thepresent compound (17)).

Yield: 10%;

¹H-NMR (CDCl₃, TMS, δ (ppm)): 2.22–2.29 (2H, m), 2.50–2.61 (2H, m), 3.68(2H, s), 6.82 (2H, dd).

PRODUCTION EXAMPLE 18

Using 5.00 g of (4-nitrobenzyl)malononitrile, 60 ml ofN,N-di-methylformamide, 1.10 g of sodium hydride (60% in oil), and 4.85g of 1-bromo-3,3,3-trifluoropropane, and according to the processdescribed in the Production Example 1, there was obtained 0.80 g of2-(4-nitrobenzyl)-2-(3,3,3-trifluoropropyl)malononitrile (the presentcompound (18)).

Yield: 11%;

¹H-NMR (CDCl₃, TMS, δ (ppm)): 2.28–2.32 (2H, m), 2.52–2.64 (2H, m), 3.40(2H, s), 7.58 (2H, d), 8.33 (2H, d).

PRODUCTION EXAMPLE 19

Using 1.00 g of (3,4-difluorobenzyl)malononitrile, 10 ml ofN,N-di-methylformamide, 0.20 g of sodium hydride (60% in oil), and 1.38g of 1-bromo-3,3,3-trifluoropropane, and according to the processdescribed in the Production Example 1, there was obtained 0.32 g of2-(3,4-difluorobenzyl)-2-(3,3,3-trifluoropropyl)malononitrile (thepresent compound (19)).

Yield: 21%;

¹H-NMR (CDCl₃, TMS, δ (ppm)): 2.20–2.29 (2H, m), 2.50–2.61 (2H, m), 3.22(2H, s), 7.11–7.15 (2H, m), 7.21–7.31 (2H, m).

PRODUCTION EXAMPLE 20

Using 0.50 g of (4-chlorobenzyl)malononitrile, 5 ml ofN,N-di-methylformamide, 0.12 g of sodium hydride (60% in oil), and 0.30ml of 1,1,3-trichloropropene, and according to the process described inthe Production Example 1, there was obtained 0.52 g of2-(4-chlorobenzyl)-2-(3,3-dichloro-2-propenyl)malononitrile (the presentcompound (20)).

Yield: 66%;

m.p.: 67.5° C.

PRODUCTION EXAMPLE 21

Using 2.00 g of (3,4-dichlorobenzyl)malononitrile, 20 ml ofN,N-di-methylformamide, 0.36 g of sodium hydride (60% in oil), and 2.37g of 1-bromo-3,3,3-trifluoropropane, and according to the processdescribed in the Production Example 1, there was obtained 0.42 g of2-(3,4-dichlorobenzyl)-2-(3,3,3-trifluoropropyl)malononitrile (thepresent compound (21)).

Yield: 45%;

¹H-NMR (CDCl₃, TMS, δ (ppm)): 2.22–2.29 (2H, m), 2.50–2.62 (2H, m), 3.21(2H, s), 7.25 (1H, d), 7.51 (2H, dd).

PRODUCTION EXAMPLE 22

Using 1.00 g of (4-cyanobenzyl)malononitrile, 10 ml ofN,N-di-methylformamide, 0.36 g of sodium hydride (60% in oil), and 2.37g of 1-bromo-3,3,3-trifluoropropane, and according to the processdescribed in the Production Example 1, there was obtained 0.42 g of2-(4-cyanobenzyl)-2-(3,3,3-trifluoropropyl)malononitrile (the presentcompound (22)).

Yield: 22%;

¹H-NMR (CDCl₃, TMS, δ (ppm)): 2.25–2.30 (2H, m), 2.51–2.62 (2H, m), 3.31(2H, s), 7.53 (2H, d), 7.76 (2H, d).

PRODUCTION EXAMPLE 23

Using 1.00 g of (4-chlorobenzyl)malononitrile, 10 ml ofN,N-di-methylformamide, 0.21 g of sodium hydride (60% in oil), and 1.44g of 4-iodo-1,1,1,2,2-pentafluorobutane, and according to the processdescribed in the Production Example 1, there was obtained 0.47 g of2-(4-chlorobenzyl)-2-(3,3,4,4,4-pentafluorobutyl)malononitrile (thepresent compound (23)).

Yield: 28%;

¹H-NMR (CDCl₃, TMS, δ (ppm)): 2.25–2.32 (2H, m), 2.41–2.53 (2H, m), 3.25(2H, s), 7.33 (2H, d), 7.43 (2H, d).

PRODUCTION EXAMPLE 24

Using 1.00 g of (4-chlorobenzyl)malononitrile, 10 ml ofN,N-di-methylformamide, 0.21 g of sodium hydride (60% in oil), and 0.67g of 1-bromo-2-fluoroethane, and according to the process described inthe Production Example 1, there was obtained 0.30 g of2-(4-chlorobenzyl)-2-(2-fluoroethyl)malononitrile (the present compound(24)).

Yield: 22%;

¹H-NMR (CDCl₃, TMS, δ (ppm)): 2.39(2H, dt), 3.27 (2H, s), 4.83 (2H, dt),7.34 (2H, d), 7.41 (2H, d).

PRODUCTION EXAMPLE 25

Using 1.0 g of (4-chlorobenzyl)malononitrile, 15 ml ofN,N-di-methylformamide, 0.073 g of cesium carbonate, and 1.47 g of2,2,3,3-tetra-fluoropropyl trifluoromethanesulfonate, and according tothe process described in the Production Example 1, there was obtained0.12 g of 2-(4-chlorobenzyl)-2-(2,2,3,3-tetrafluoropropyl)malononitrile(the present compound (25)).

Yield: 7%;

¹H-NMR (CDCl₃, TMS, δ (ppm)): 2.69 (2H, t), 3.31 (2H, s), 5.87 (1H, tt),7.34 (2H, d), 7.41 (2H, d).

PRODUCTION EXAMPLE 26

First, 0.55 g of 4-iodobenzyl bromide was dissolved in 10 ml ofN,N-dimethylformamide, to which the suspension of 0.11 g of sodiumhydride (60% in oil) and 0.30 g of (3,3,3-trifluoropropyl)malononitrilein 5 ml of N,N-dimethylformamide was added dropwise, while stirringunder ice cooling. After stirring for 4 hours at 0° C., 10% hydrochloricacid was added to the reaction mixture at room temperature, which wasextracted with ethyl acetate. The organic layer was successively washedwith water, a saturated aqueous sodium chloride solution, dried overanhydrous magnesium sulfate, and then concentrated under reducedpressure. The residue was subjected to silica gel column chromatographyto give 0.16 g of2-(4-iodobenzyl)-2-(3,3,3-trifluoropropyl)malononitrile (the presentcompound (26)).

Yield: 22%;

¹H-NMR (CDCl₃, TMS, δ (ppm)): 2.17–2.23 (2H, m), 2.49–2.60 (2H, m), 3.22(2H, s), 7.11 (2H, d), 7.78 (2H, d).

PRODUCTION EXAMPLE 27

Using 0.15 g of (4-vinylbenzyl)chloride, 3 ml of N,N-dimethylformamide,0.05 g of sodium hydride (60% in oil) and 0.17 g of(3,3,3-trifluoropropyl)malononitrile, and according to the processdescribed in the Production Example 27, there was obtained 0.18 g of2-(3,3,3-trifluoropropyl)-2-(4-vinylbenzyl)malononitrile (the presentcompound (27)).

Yield: 63%;

¹H-NMR (CDCl₃, TMS, δ (ppm)): 2.20–2.24 (2H, m), 2.48–2.63 (2H, m), 3.26(2H, s), 5.32 (2H, d), 5.80 (2H, d), 6.72 (2H, dd), 7.33 (2H, d), 7.41 (d).

PRODUCTION EXAMPLE 28

Using 0.20 g of (4-(trifluoromethoxy)benzyl)malononitrile, 5 ml ofN,N-dimethylformamide, 50 mg of sodium hydride (60% in oil), and 0.17 mlof 1,1,3-trichloropropene, and according to the process described in theProduction Example 1, there was obtained 80 mg of2-(3,3-dichloro-2-propenyl)-2-(4-(trifluoromethoxy)benzyl)malononitrile(the present compound (28)).

Yield: 28%;

m.p.: 96.5° C.

PRODUCTION EXAMPLE 29

Using 0.20 g of (4-(trifluoromethoxy)benzyl)malononitrile, 5 ml ofN,N-dimethylformamide, 50 mg of sodium hydride (60% in oil), and 0.46 gof 1,1,3-tribromopropene, and according to the process described in theProduction Example 1, there was obtained 0.16 g of2-(3,3-dibromo-2-propenyl)-2-(4-(trifluoromethoxy)benzyl)malononitrile(the present compound (29)).

Yield: 44%;

m.p.: 126.7° C.

PRODUCTION EXAMPLE 30

Using 0.23 g of 3-nitro-4-methylbenzyl bromide, 3 ml ofN,N-di-methylformamide, 0.05 g of sodium hydride (60% in oil), and 0.17g of (3,3,3-trifluoropropyl)malononitrile, and according to the processdescribed in the Production Example 26, there was obtained 0.10 g of2-(3-nitro-4-methylbenzyl)-2-(3,3,3-trifluoropropyl)malononitrile (thepresent compound (30)).

Yield: 31%;

¹H-NMR (CDCl₃, TMS, δ (ppm)): 2.25–2.30 (2H, m), 2.49–2.61 (2H, m), 2.65(3H, s), 3.31 (2H, s), 7.45 (1H, d), 7.55 (1H, d), 8.00 (1H, s).

PRODUCTION EXAMPLE 31

Using 0.16 g of 4-ethylbenzyl chloride, 3 ml of N,N-dimethylformamide,0.05 g of sodium hydride (60% in oil), and 0.17 g of(3,3,3-trifluoropropyl)malononitrile, and according to the processdescribed in the Production Example 26, there was obtained 0.14 g of2-(4-ethylbenzyl)-2-(3,3,3-trifluoropropyl)malononitrile (the presentcompound (31)).

Yield: 50%;

¹H-NMR (CDCl₃, TMS, δ (ppm)): 1.25 (3H, t), 2.04–2.23 (2H, m), 2.50–2.58(2H, m), 3.23 (2H, s), 7.24–7.28 (4H, m).

PRODUCTION EXAMPLE 32

Using 0.20 g of 3-methoxybenzyl bromide, 3 ml of N,N-dimethylformamide,0.05 g of sodium hydride (60% in oil), and 0.17 g of(3,3,3-trifluoropropyl)malononitrile, and according to the processdescribed in the Production Example 26, there was obtained 0.09 g of2-(3-methoxybenzyl)-2-(3,3,3-trifluoropropyl)malononitrile (the presentcompound (32)).

Yield: 33%;

¹H-NMR (CDCl₃, TMS, δ (ppm)): 2.19–2.22 (2H, m), 2.48–2.59 (2H, m), 3.24(2H, s), 3.83 (3H, s), 6.90–7.00 (3H, m), 7.31 (1H, m).

PRODUCTION EXAMPLE 33

Using 0.23 g of 4-t-butylbenzyl bromide, 3 ml of N,N-dimethylformamide,0.05 g of sodium hydride (60% in oil), and 0.17 g of(3,3,3-trifluoropropyl)malononitrile, and according to the processdescribed in the Production Example 26, there was obtained 0.14 g of2-(4-t-butylbenzyl)-2-(3,3,3-trifluoropropyl)malononitrile (the presentcompound (33)).

Yield: 47%;

¹H-NMR (CDCl₃, TMS, δ (ppm)): 1.33 (9H, s), 2.20–2.24 (2H, m), 2.48–2.59(2H, m), 3.24 (2H, s), 7.29 (2H, d), 7.43 (2H, d).

PRODUCTION EXAMPLE 34

Using 0.22 g of 4-(methylthio)benzyl bromide, 3 ml ofN,N-dimethylformamide, 0.05 g of sodium hydride (60% in oil), and 0.17 gof (3,3,3-trifluoropropyl)malononitrile, and according to the processdescribed in the Production Example 26, there was obtained 0.15 g of2-(4-(methylthio)benzyl)-2-(3,3,3-trifluoropropyl)malononitrile (thepresent compound (34)).

Yield: 50%;

¹H-NMR (CDCl₃, TMS, δ (ppm)): 2.17–2.22 (2H, m), 2.43–2.53 (2H, m), 2.50(3H, s), 3.16 (2H, s), 7.29 (4H, s).

PRODUCTION EXAMPLE 35

Using 0.21 g of 4-isopropylbenzyl bromide, 3 ml ofN,N-dimethylformamide, 0.05 g of sodium hydride (60% in oil), and 0.17 gof (3,3,3-trifluoropropyl)malononitrile, and according to the processdescribed in the Production Example 26, there was obtained 0.24 g of2-(4-isopropylbenzyl)-2-(3,3,3-trifluoropropyl)malononitrile (thepresent compound (35)).

Yield: 85%;

¹H-NMR (CDCl₃, TMS, δ (ppm)): 1.27 (6H, d), 2.20–2.23 (2H, m), 2.51–2.60(2H, m), 3.36 (2H, s), 7.26 (4H, s).

PRODUCTION EXAMPLE 36

Using 0.24 g of 3-(trifluoromethyl)benzyl bromide, 3 ml ofN,N-dimethylformamide, 0.05 g of sodium hydride (60% in oil), and 0.17 gof (3,3,3-trifluoropropyl)malononitrile, and according to the processdescribed in the Production Example 26, there was obtained 0.17 g of2-(3-(trifluoromethyl)benzyl)-2-(3,3,3-trifluoropropyl)malononitrile(the present compound (36)).

Yield: 53%;

¹H-NMR (CDCl₃, TMS, δ (ppm)): 2.21–2.29 (2H, m), 2.48–2.62 (2H, m), 3.33(2H, s), 7.52–7.72 (3H, m).

PRODUCTION EXAMPLE 37

Using 0.14 g of 3-metylbenzyl chloride, 3 ml of N,N-dimethylformamide,0.05 g of sodium hydride (60% in oil), and 0.17 g of(3,3,3-trifluoropropyl)malononitrile, and according to the processdescribed in the Production Example 26, there was obtained 0.17 g of2-(3-methylbenzyl)-2-(3,3,3-trifluoropropyl)malononitrile (the presentcompound (37)).

Yield: 62%;

¹H-NMR (CDCl₃, TMS, δ (ppm)): 2.18–2.23 (2H, m), 2.36 (3H, s), 2.47–2.59(2H, m), 3.23 (2H, s), 7.16 (1H, s)7.22–7.33 (3H, m).

PRODUCTION EXAMPLE 38

Using 0.21 g of 2-chloro-4-nitrobenzyl chloride, 3 ml ofN,N-di-methylformamide, 0.05 g of sodium hydride (60% in oil), and 0.17g of (3,3,3-trifluoropropyl)malononitrile, and according to the processdescribed in the Production Example 26, there was obtained 0.15 g of2-(2-chloro-4-nitrobenzyl)-2-(3,3,3-trifluoropropyl)malononitrile (thepresent compound (38)).

Yield: 46%;

¹H-NMR (CDCl₃, TMS, δ (ppm)): 2.32–2.36 (2H, m), 2.49–2.60 (2H, m), 3.60(2H, s), 7.60 (1H, d), 8.23 (1H, d), 8.39 (1H, s).

PRODUCTION EXAMPLE 39

Using 0.28 g of 3-chloro-4-(trifluoromethyl)benzyl chloride, 3 ml ofN,N-dimethylformamide, 0.05 g of sodium hydride (60% in oil), and 0.17 gof (3,3,3-trifluoropropyl)malononitrile, and according to the processdescribed in the Production Example 26, there was obtained 0.25 g of2-(3-chloro-4-(trifluoromethyl)benzyl)-2-(3,3,3-trifluoropropyl)malononitrile(the present compound (39)).

Yield: 70%;

¹H-NMR (CDCl₃, TMS, δ (ppm)): 2.26–2.30 (2H, m), 2.52–2.63 (2H, m), 3.28(2H, s), 7.24 (1H, d), 7.29 (1H, d), 7.70 (1H, dd).

PRODUCTION EXAMPLE 40

Using 0.23 g of 2,3-dimethoxybenzyl bromide, 3 ml ofN,N-di-methylformamide, 0.05 g of sodium hydride (60% in oil), and 0.17g of (3,3,3-trifluoropropyl)malononitrile, and according to the processdescribed in the Production Example 26, there was obtained 0.26 g of2-(2,3-dimethoxybenzyl)-2-(3,3,3-trifluoropropyl)malononitrile (thepresent compound (40)).

Yield: 80%;

¹H-NMR (CDCl₃, TMS, δ (ppm)): 2.18–2.22 (2H, m), 2.46–2.57 (2H, m), 3.37(2H, s), 3.88 (3H, s), 3.90 (3H, s), 6.95–7.11 (2H, d).

PRODUCTION EXAMPLE 41

Using 0.10 g of 2-chloro-4-(trifluoromethyl)benzyl bromide, 3 ml ofN,N-dimethylformamide, 0.05 g of sodium hydride (60% in oil), and. 0.17g of (3,3,3-trifluoropropyl)malononitrile, and according to the processdescribed in the Production Example 26, there was obtained 0.05 g of2-(2-chloro-4-(trifluoromethyl)benzyl)-2-(3,3,3-trifluoropropyl)malononitrile(the present compound (41)).

Yield: 39%;

¹H-NMR (CDCl₃, TMS, δ (ppm)): 2.21–2.35 (2H, m), 2.49–2.63 (2H, m), 3.56(2H, s), 7.62 (1H, d), 7.68 (1H, d), 7.78 (1H, s).

PRODUCTION EXAMPLE 42

Using 2.05 g of 2-(1-(4-chlorophenyl)ethyl)malononitrile, 10 ml ofN,N-dimethylformamide, 1.38 g of potassium carbonate, and 1.77 g of1-bromo-3,3,3-trifluoropropane, and according to the process describedin the Production Example 1, there was obtained 0.49 g of2-(1-(4-chlorophenyl)ethyl)-2-(3,3,3-trifluoropropyl)malononitrile (thepresent compound (42)).

Yield: 17%;

¹H-NMR (CDCl₃, TMS, δ (ppm)): 1.71 (3H, d), 1.86–2.14 (2H,m), 2.40–2.60(2H,m), 3.22 (1H,q), 7.27 (2H,d), 7.39 (2H,d).

PRODUCTION EXAMPLE 43

First, 1.00 g of2-(3,3,3-trifluoropropyl)-2-(4-vinylbenzyl)malononitrile (the presentcompound (27)) was dissolved in 10 ml of chloroform, to which 0.5 g ofbromine dissolved in 8 ml of chloroform was added dropwise slowly, whilestirring under ice cooling, followed by further stirring for 5 hours.Then, water was added to the reaction mixture, which was extracted withchloroform. The organic layer was successively washed with water and asaturated aqueous sodium chloride solution, dried over anhydrousmagnesium sulfate, and then concentrated under reduced pressure. Theresidue was subjected to silica gel column chromatography to give 1.07 gof 2-(4-(1,2-dibromoethyl)benzyl)-2-(3,3,3-trifluoropropyl)malononitrile(the present compound (43)).

Yield: 68%;

¹H-NMR (CDCl₃, TMS, δ (ppm)): 2.22–2.26 (2H, m), 2.49–2.61 (2H, m), 3.27(2H, s), 3.97 (1H, t), 4.07 (1H, dd), 5.14 (1H, dd), 7.39 (2H, d), 7.48(2H, d).

PRODUCTION EXAMPLE 44

Using 0.51 g of (2-chloro-4-fluorobenzyl)malononitrile, 5 ml ofN,N-dimethylformamide, 0.12 g of sodium hydride (60% in oil), and 0.34 gof 1-bromo-3,3,3-trifluoropropane, and according to the processdescribed in the Production Example 1, there was obtained 0.21 g of2-(2-chloro-4-fluorobenzyl)-2-(3,3,3-trifluoropropyl)malononitrile (thepresent compound (44)).

Yield: 34%;

¹H-NMR (CDCl₃, TMS, δ (ppm)): 2.27–2.31 (2H, m), 2.50–2.62 (2H, m), 3.48(2H, s), 7.07 (1H, m), 7.26 (1H, m), 7.53 (1H, m).

PRODUCTION EXAMPLE 45

Using 0.49 g of 3-metyl-4-nitrobenzyl methanesulfonate, 5 ml ofN,N-dimethylformamide, 0.10 g of sodium hydride (60% in oil), and 0.3 gof (3,3,3-trifluoropropyl)malononitrile, and according to the processdescribed in the Production Example 26, there was obtained 0.51 g of2-(3-methyl-4-nitrobenzyl)-2-(3,3,3-trifluoropropyl)malononitrile (thepresent compound (45)).

Yield: 82%;

¹H-NMR (CDCl₃, TMS, δ (ppm)): 2.14–2.30 (2H, m), 2.51–2.65 (2H, m), 2.66(3H, s), 7.37 (1H, d), 7.39 (1H, d), 8.03 (1H, dd).

PRODUCTION EXAMPLE 46

Using 0.32 g of (4-cyanobenzyl)malononitrile, 7 ml ofN,N-di-methylformamide, 0.12 g of sodium hydride (60% in oil), and 0.25g of 1-bromo-2-fluoroethane, and according to the process described inthe Production Example 1, there was obtained 0.10 g of2-(4-cyanobenzyl)-2-(2-fluoroethyl)malononitrile (the present compound(46)).

Yield: 22%;

¹H-NMR (CDCl₃, TMS, δ (ppm)): 2.45 (2H, dt), 3.36 (2H, s), 4.85 (2H,dt), 7.55 (2H, d), 7.75 (2H, d).

PRODUCTION EXAMPLE 47

Using 0.40 g of (4-nitrobenzyl)malononitrile, 5 ml ofN,N-dimethylformamide, 0.12 g of sodium hydride (60% in oil), and 0.25 gof 1-bromo-2-fluoroethane, and according to the process described in theProduction Example 1, there was obtained 0.10 g of2-(4-nitrobenzyl)-2-(2-fluoroethyl)malononitrile (the present compound(47)).

Yield: 22%;

¹H-NMR (CDCl₃, TMS, δ (ppm)): 2.47 (2H, dt), 3.41 (2H, s), 4.86 (2H,dt), 7.61 (2H, d), 8.30 (2H, d).

PRODUCTION EXAMPLE 48

Using 0.50 g of (4-(trifluoromethoxy)benzyl)malononitrile, 9 ml ofN,N-dimethylformamide, 96 mg of sodium hydride (60% in oil), and 0.79 gof 4-bromo-1,1,2-trifluoro-1-butene, and according to the processdescribed in the Production Example 1, there was obtained 0.19 g of2-(3,4,4-trifluoro-3-butenyl)-2-(4-(trifluoromethoxy)benzyl)malononitrile(the present compound (49)).

Yield: 27%;

¹H-NMR (CDCl₃, TMS, δ (ppm)): 2.19–2.26(2H, m), 2.66–2.81(2H, m),3.26(2H, s), 7.28(2H, d), 7.43(2H, d).

PRODUCTION EXAMPLE 49

Using 0.50 g of (4-(trifluoromethoxy)benzyl)malononitrile, 8 ml ofN,N-dimethylformamide, 96 mg of sodium hydride (60% in oil), and 0.74 gof 1-bromo-3,3,3-trifluoropropane, and according to the processdescribed in the Production Example 1, there was obtained 0.14 g of2-(3,3,3-trifluoropropyl)-2-(4-(trifluoromethoxy)benzyl)malononitrile(the present compound (50)).

Yield: 21%;

¹H-NMR (CDCl₃, TMS, δ (ppm)): 2.21–2.28 (2H, m), 2.46–2.61 (2H, m), 3.27(2H, s), 7.27 (2H, d), 7.44 (2H, d).

PRODUCTION EXAMPLE 50

Using 0.47 g of (4-bromobenzyl)malononitrile, 5 ml ofN,N-di-methylformamide, 0.12 g of sodium hydride (60% in oil), and 0.25g of 1-bromo-2-fluoroethane, and according to the process described inthe Production Example 1, there was obtained 0.27 g of2-(4-bromobenzyl)-2-(2-fluoroethyl)malononitrile (the present compound(51)).

Yield: 48%;

¹H-NMR (CDCl₃, TMS, δ (ppm)): 2.39 (2H, dt), 3.26 (2H, s), 4.83 (2H,dt), 7.22 (2H, d), 7.55 (2H, d).

PRODUCTION EXAMPLE 51

Using 0.37 g of (4-methoxybenzyl)malononitrile, 5 ml ofN,N-dimethylformamide, 0.12 g of sodium hydride (60% in oil), and 0.25 gof 1-bromo-2-fluoroethane, and according to the process described in theProduction Example 1, there was obtained 0.23 g of2-(2-fluoroethyl)-2-(4-methoxybenzyl)malononitrile (the present compound(52)).

Yield: 49%;

¹H-NMR (CDCl₃, TMS, δ (ppm)): 2.35 (2H, dt), 3.22 (2H, s), 3.76 (3H, s),4.80 (2H, dt), 6.91 (2H, d), 7.28 (2H, d).

PRODUCTION EXAMPLE 52

Using 0.41 g of 2-(1-(4-chlorophenyl)ethyl)malononitrile, 5 ml ofN,N-dimethylformamide, 0.12 g of sodium hydride (60% in oil), and 0.25 gof 1-bromo-2-fluoroethane, and according to the process described in theProduction Example 1, there was obtained 0.22 g of2-(1-(4-chlorophenyl)ethyl)-2-(2-fluoroethyl)malononitrile (the presentcompound (53)).

Yield: 44%;

¹H-NMR (CDCl₃, TMS, δ (ppm)): 1.71 (3H, d), 2.04–2.33 (2H, m)3.30 (1H,q), 4.80 (2H, dt), 7.28 (2H, d), 7.37 (2H, d).

PRODUCTION EXAMPLE 53

Using 0.50 g of (4-(trifluoromethylthio)benzyl)malononitrile, 10 ml ofN,N-dimethylformamide, 86 mg of sodium hydride (60% in oil), and 0.74 gof 4-bromo-1,1,2-trifluoro-1-butene, and according to -the processdescribed in the Production Example 1, there was obtained 0.12 g of2-(3,4,4-trifluoro-3-butenyl)-2-(4-(trifluoromethylthio)benzyl)malononitrile(the present compound (54)).

Yield: 17%;

¹H-NMR (CDCl₃, TMS, δ (ppm)): 2.20–2.27 (2H, m), 2.68–2.82 (2H, m), 3.28(2H, s), 7.45 (2H, d), 7.72 (2H, d).

PRODUCTION EXAMPLE 54

Using 0.45 g of (4-(trifluoromethyl)benzyl)malononitrile, 5 ml ofN,N-dimethylformamide, 0.12 g of sodium hydride (60% in oil), and 0.25 gof 1,1,3-trichloropropene, and according to the process described in theProduction Example 1, there was obtained 0.28 g of2-(3,3-dichloro-2-propenyl)-2-(4-(trifluoromethyl)benzyl)malononitrile(the present compound (55)).

Yield: 37%;

¹H-NMR (CDCl₃, TMS, δ (ppm)): 2.96 (2H, d), 3.28 (2H, s), 6.09 (1H, d),7.53 (2H, d), 7.70 (2H, d).

PRODUCTION EXAMPLE 55

Using 0.37 g of (4-cyanobenzyl)malononitrile, 5 ml ofN,N-dimethylformamide, 0.12 g of sodium hydride (60% in oil), and 0.25 gof 1,3,3-trichloropropene, and according to the process described in theProduction Example 1, there was obtained 0.17 g of2-(4-cyanobenzyl)-2-(3,3-dichloropropenyl)malononitrile (the presentcompound (56)).

Yield: 29%;

¹H-NMR (CDCl₃, TMS, δ (ppm)): 2.97 (2H, d), 3.24 (2H, s), 6.08 (1H, d),7.53 (2H, d), 7.64 (2H, d).

PRODUCTION EXAMPLE 56

Using 0.48 g of 2-(1-(4-(trifluoromethyl)phenyl)ethyl)malononitrile, 5ml of N,N-dimethylformamide, 0.12 g of sodium hydride (60% in oil), and0.34 g of 1-bromo-3,3,3-trifluoropropane, and according to the processdescribed in the Production Example 1, there was obtained 0.26 g of2-(1-(4-(trifluoromethyl)phenyl)ethyl-2-(3,3,3-trifluoropropyl)malononitrile(the present compound (57)).

Yield: 39%;

¹H-NMR (CDCl₃, TMS, δ (ppm)): 1.76 (3H, d), 1.90–2.23 (2H, m), 2.43–2.96(2H, m), 3.32 (1H, q), 7.48 (2H, d), 7.71 (2H, d).

PRODUCTION EXAMPLE 57

First, 0.2 g of(2-(4-(1,2-dibromoethyl)benzyl)-2-(3,3,3-trifluoropropyl)malononitrile(the present compound (43)) was dissolved in 5 ml ofN,N-dimethylformamide, to which 0.1 g of potassium t-butoxide was added,while stirring under ice cooling. After stirring for 5 hours at roomtemperature, water was added to the reaction mixture, which wasextracted with ethyl acetate. The organic layer was successively washedwith water, a saturated aqueous sodium chloride solution, dried overanhydrous magnesium sulfate, and then concentrated under reducedpressure. The residue was subjected to silica gel column chromatographyto give 0.05 g of2-(4-(2-bromovinyl)benzyl)-2-(3,3,3-trifluoropropyl)malononitrile (thepresent compound (58)).

Yield: 41%;

¹H-NMR (CDCl₃, TMS, δ (ppm)): 2.20–2.26 (2H, m), 2.49–2.61 (2H, m), 3.27(2H, s), 3.51 (2H, s), 5.84 (1H, d), 6.17 (1H, d), 7.34 (2H, d), 7.68(2H, d).

PRODUCTION EXAMPLE 58

Using 0.37 g of (4-fluorobenzyl)malononitrile, 5 ml ofN,N-dimethylformamide, 0.12 g of sodium hydride (60% in oil), and 0.25 gof 1-bromo-2-fluoroethane, and according to the process described in theProduction Example 1, there was obtained 0.22 g of2-(4-fluorobenzyl)-2-(2-fluoroethyl)malononitrile (the present compound(59)).

Yield: 49%;

¹H-NMR (CDCl₃, TMS, δ (ppm)): 2.40 (2H, dt), 3.28 (2H, s), 4.83 (2H,dt), 7.04–7.14 (2H, m), 7.36–7.40 (2H, m).

PRODUCTION EXAMPLE 59

Using 0.49 g of benzylmalononitrile, 15 ml of N,N-dimethylformamide,0.14 g of sodium hydride (60% in oil), and 0.33 g of1,3-dichloropropene, and according to the process described in theProduction Example 1, there was obtained 0.25 g of2-benzyl-2-((E)-3-chloro-2-propenyl)malononitrile (the present compound(60)) as high-polar compound.

Yield: 36%;

¹H-NMR (CDCl₃, TMS, δ (ppm)): 2.71 (2H, d), 3.21 (2H, s), 6.06 (1H, dt),6.37 (1H, d), 7.36–7.45 (5H, m).

And there was obtained 0.28 g of2-benzyl-2-((Z)-3-chloro-2-propenyl)malononitrile (the present compound(61)) as low-polar compound.

Yield: 40%;

¹H-NMR (CDCl₃, TMS, δ (ppm)): 2.98 (2H, d), 3.26 (2H, s), 6.00 (1H, dt),6.49 (1H, d), 7.37–7.52 (5H, m).

PRODUCTION EXAMPLE 60

Using 0.30 g of (3,4,4-trifluoro-3-butenyl)malononitrile, 5 ml ofN,N-dimethylformamide, 75 mg of sodium hydride (60% in oil), and 0.52 gof 2-chloro-4-(trifluoromethyl)benzylbromide, and according to theprocess described in the Production Example 1, there was obtained 0.28 gof2-(2-chloro-4-(trifluoromethyl)benzyl)-2-(3,4,4-trifluoro-3-butenyl)malononitrile(the present compound (62)).

Yield: 45%;

¹H-NMR (CDCl₃, TMS, δ (ppm)): 2.30 (2H, t), 2.66–2.88 (2H, m), 3.56 (2H,s), 7.63 (1H, d), 7.70 (1H, d), 7.75 (1H, s).

PRODUCTION EXAMPLE 61

Using 1.01 g of (3-chlorobenzyl)malononitrile, 5 ml ofN,N-dimethylformamide, 1.38 g of potassium carbonate, and 1.44 g of1-bromo-2-chloroethane, and according to the process described in theProduction Example 1, there was obtained 0.60 g of2-(3-chlorobenzyl)-2-(2-chloroethyl)malononitrile (the present compound(63)).

Yield: 23%;

¹H-NMR (CDCl₃, TMS, δ (ppm)): 2.44 (2H, dd), 3.25 (2H, s), 3.81 (2H,dd), 7.27–7.43 (4H, m).

PRODUCTION EXAMPLE 62

Using 0.23 g of (4-(trifluoromethyl)benzyl)malononitrile, 3 ml ofN,N-dimethylformamide, 0.05 g of sodium hydride (60% in oil), and 0.13 gof 1-bromo-2-fluoroethane, and according to the process described in theProduction Example 1, there was obtained 0.12 g of2-(2-fluoroethyl)-2-(4-(trifluoromethyl)benzyl)malononitrile (thepresent compound (64)).

Yield: 48%;

¹H-NMR (CDCl₃, TMS, δ (ppm)): 2.43 (2H, dt), 3.58 (2H, s), 4.85 (2H,dt), 7.54 (2H, d), 7.70 (2H, d).

PRODUCTION EXAMPLE 63

Using 0.24 g of (3-bromobenzyl)malononitrile, 3 ml ofN,N-dimethylformamide, 0.10 g of sodium hydride (60% in oil), and 0.13 gof 1-bromo-2-fluoroethane, and according to the process described in theProduction Example 1, there was obtained 0.11 g of2-(3-bromobenzyl)-2-(2-fluoroethyl)malononitrile (the present compound(65)).

Yield: 33%;

¹H-NMR (CDCl₃, TMS, δ (ppm)): 2.38 (2H, dt), 3.26 (2H, s), 3.83 (3H, s),4.86 (2H, dt), 7.27–7.37 (2H, m)7.54–7.57 (2H, m).

PRODUCTION EXAMPLE 64

Using 0.15 g of (3,4,4-trifluoro-3-butenyl)malononitrile, 5 ml ofN,N-dimethylformamide, 38 mg of sodium hydride (60% in oil), and 0.27 gof 2,6-dichloro-4-(trifluoromethyl)benzylbromide, and according to theprocess described in the Production Example 1, there was obtained 0.18 gof2-(2,6-dichloro-4-(trifluoromethyl)benzyl)-2-(3,4,4-trifluoro-3-butenyl)malononitrile(the present compound (66)).

Yield: 51%;

¹H-NMR (CDCl₃, TMS, δ (ppm)): 2.39–2.45 (2H, m), 2.71–2.83 (2H, m), 3.80(2H, s), 7.70 (2H, s).

PRODUCTION EXAMPLE 65

Using 0.25 g of (4-bromo-2-fluorobenzyl)malononitrile, 3 ml ofN,N-dimethylformamide, 0.10 g of sodium hydride (60% in oil), and 0.13 gof 1-bromo-2-fluoroethane, and according to the process described in theProduction Example 1, there was obtained 0.10 g of2-(4-bromo-2-fluorobenzyl)-2-(2-fluoroethyl)malononitrile (the presentcompound (67)).

Yield: 33%;

¹H-NMR (CDCl₃, TMS, δ (ppm)): 2.41 (2H, dt), 3.35 (2H, s), 4.82 (2H,dt), 7.32–7.42 (3H, m).

PRODUCTION EXAMPLE 66

Using 0.20 g of (3,4,4-trifluoro-3-butenyl)malononitrile, 5 ml ofN,N-dimethylformamide, 50 mg of sodium hydride (60% in oil), and 0.25 gof α-bromo-p-tolunitrile, and according to the process described in theProduction Example 1, there was obtained 0.21 g of2-(4-cyanobenzyl)-2-(3,4,4-trifluoro-3-butenyl)malononitrile (thepresent compound (68)).

Yield: 63%;

¹H-NMR (CDCl₃, TMS, δ (ppm)): 2.21–2.32 (2H, m), 2.68–2.87 (2H, m), 3.31(2H, s), 7.54 (2H, d), 7.72 (2H, d).

PRODUCTION EXAMPLE 67

Using 0.24 g of (2-bromobenzyl)malononitrile, 3 ml ofN,N-dimethylformamide, 0.10 g of sodium hydride (60% in oil), and 0.13 gof 1-bromo-2-fluoroethane, and according to the process described in theProduction Example 1, there was obtained 0.12 g of2-(2-bromobenzyl)-2-(2-fluoroethyl)malononitrile (the present compound(69)).

Yield: 37%;

¹H-NMR (CDCl₃, TMS, δ (ppm)): 2.47 (2H, dt), 3.58 (2H, s), 4.82 (2H,dt), 7.24 (1H, dd), 7.28 (1H, dd), 7.58 (1H, d), 7.65 (1H, d).

PRODUCTION EXAMPLE 68

Using 0.21 g of 2,4-difluorobenzyl bromide, 3 ml ofN,N-dimethylformamide, 0.05 g of sodium hydride (60% in oil), and 0.17 gof (3,3,3-trifluoropropyl)malononitrile, and according to the processdescribed in the Production Example 26, there was obtained 0.17 g of2-(2,4-difluorobenzyl)-2-(3,3,3-trifluoropropyl)malononitrile (thepresent compound (70)).

Yield: 57%;

¹H-NMR (CDCl₃, TMS, δ (ppm)): 2.21–2.26 (2H, m), 2.47–2.59 (2H, m), 3.34(2H, s), 6.91–7.02 (2H, m), 7.40–7.47 (2H, m).

PRODUCTION EXAMPLE 69

Using 0.21 g of 3,5-difluorobenzyl bromide, 3 ml ofN,N-dimethyl-formamide, 0.05 g of sodium hydride (60% in oil), and 0.17g of (3,3,3-trifluoropropyl)malononitrile, and according to the processdescribed in the Production Example 26, there was obtained 0.21 g of2-(3,5-difluorobenzyl)-2-(3,3,3-trifluoropropyl)malononitrile (thepresent compound (71)).

Yield: 73%;

¹H-NMR (CDCl₃, TMS, δ (ppm)): 2.22–2.28 (2H, m), 2.49–2.61 (2H, m), 3.23(2H, s), 6.87–6.95 (3H, m).

PRODUCTION EXAMPLE 70

Using 1.0 g of (4-(trifluoromethyl)benzyl)malononitrile, 8 ml ofN,N-dimethylformamide, 0.73 g of cesium carbonate, and 1.0 g of2,2,2-trifluoroethyl trifluoromethanesulfonate, and according to theprocess described in the Production Example 1, there was obtained 0.58 gof 2-(2,2,2-trifluoroethyl)-2-(4-(trifluoromethyl)benzyl)malononitrile(the present compound (72)).

Yield: 40%;

¹H-NMR (CDCl₃, TMS, δ (ppm)): 2.84 (2H, q), 3.40 (2H, d), 7.55 (2H, d),7.72 (2H, d).

PRODUCTION EXAMPLE 71

Using 0.50 g of (4-(trifluoromethyl)benzyl)malononitrile, 6 ml ofN,N-dimethylformamide, 98 mg of sodium hydride (60% in oil), and 0.46 gof 4-bromo-1,1,2-trifluoro-1-butene, and according to the processdescribed in the Production Example 1, there was obtained 0.16 g of2-(3,4,4-trifluoro-3-butenyl)-2-(4-(trifluoromethyl)benzyl)malononitrile(the present compound (73)).

Yield: 21%;

¹H-NMR (CDCl₃, TMS, δ (ppm)): 2.21–2.27 (2H, m), 2.70–2.79 (2H, m), 3.31(2H, s), 7.52 (2H, d), 7.71 (2H, d).

PRODUCTION EXAMPLE 72

Using 0.50 g of (4-(trifluoromethyl)benzyl)malononitrile, 6 ml ofN,N-dimethylformamide, 98 mg of sodium hydride (60% in oil), and 0.43 gof 1-bromo-3,3,3-trifluoropropane, and according to the processdescribed in the Production Example 1, there was obtained 0.30 g of2-(3,3,3-trifluoropropyl)-2-(4-(trifluoromethyl)benzyl)malononitrile(the present compound (74)).

Yield: 40%;

¹H-NMR (CDCl₃, TMS, δ (ppm)): 2.23–2.30 (2H, m), 2.47–2.66 (2H, m), 3.32(2H, s), 7.52 (2H, d), 7.71 (2H, d).

PRODUCTION EXAMPLE 73

Using 0.19 g of 2-fluorobenzyl bromide, 3 ml of N,N-dimethylformamide,0.05 g of sodium hydride (60% in oil), and 0.17 g of(3,3,3-trifluoropropyl)malononitrile, and according to the processdescribed in the Production Example 26, there was obtained 0.17 g of2-(2-fluorobenzyl)-2-(3,3,3-trifluoropropyl)malononitrile (the presentcompound (75)).

Yield: 63%;

¹H-NMR (CDCl₃, TMS, δ (ppm)): 2.20–2.26 (2H, m), 2.46–2.62 (2H, m), 3.38(2H, s), 7.14–7.45 (4H, m).

PRODUCTION EXAMPLE 74

Using 0.50 g of (4-(trifluoromethyl)benzyl)malononitrile, 5 ml ofN,N-dimethylformamide, 363 mg of cesium carbonate, and 0.63 g of2,2,3,3,3-pentafluoropropyl trifluoromethanesulfonate, and according tothe process described in the Production Example 1, there was obtained0.20 g of2-(2,2,3,3,3-pentafluoropropyl)-2-(4-(trifluoromethyl)benzyl)malononitrile(the present compound (76)).

Yield: 34%;

¹H-NMR (CDCl₃, TMS, δ (ppm)): 2.78 (2H, t), 3.43 (2H, s), 7.56 (2H, d),7.75 (2H, d).

PRODUCTION EXAMPLE 75

Using 0.50 g of (4-(trifluoromethyl)benzyl)malononitrile, 5 ml ofN,N-dimethylformamide, 59 mg of sodium hydride (60% in oil), and 0.77 gof 2,2,3,3,4,4,4-heptafluorobutyl trifluoromethanesulfonate, andaccording to the process described in the Production Example 1, therewas obtained 73 mg of2-(2,2,3,3,4,4,4-heptafluorobutyl)-2-(4-(trifluoromethyl)benzyl)malononitrile(the present compound (77)).

Yield: 8%;

¹H-NMR (CDCl₃, TMS, δ (ppm)): 2.82 (2H, t), 3.43 (2H, s), 7.56 (2H, d),7.73 (2H, d).

PRODUCTION EXAMPLE 76

Using 0.50 g of (4-(trifluoromethyl)benzyl)malononitrile, 5 ml ofN,N-dimethylformamide, 88 mg of sodium hydride (60% in oil), and 0.53 gof 1-iodo-4,4,4-trifluorobutane, and according to the process describedin the Production Example 1, there was obtained 0.25 g of2-(4,4,4-trifluorobutyl)-2-(4-(trifluoromethyl)benzyl)malononitrile (thepresent compound (78)).

Yield: 30%;

¹H-NMR (CDCl₃, TMS, δ (ppm)): 1.99–2.39 (4H, m), 2.18–2.24 (2H, m), 3.26(2H, s), 7.49 (2H, d), 7.67 (2H, d).

PRODUCTION EXAMPLE 77

Using 0.15 g of 3-fluorobenzyl chloride, 3 ml of N,N-dimethylformamide,0.05 g of sodium hydride (60% in oil), and 0.17 g of(3,3,3-trifluoropropyl)malononitrile, and according to the processdescribed in the Production Example 26, there was obtained 0.11 g of2-(3-fluorobenzyl)-2-(3,3,3-trifluoropropyl)malononitrile (the presentcompound (79)).

Yield: 41%;

¹H-NMR (CDCl₃, TMS, δ (ppm)): 2.21–2.26 (2H, m), 2.47–2.57 (2H, m), 3.26(2H, s), 7.08–7.18 (3H, m), 7.38–7.45 (1H, m).

PRODUCTION EXAMPLE 78

Using 0.26 g of 2,3,4,5,6-pentafluoaobenzyl bromide, 3 ml ofN,N-dimethylformamide, 0.05 g of sodium hydride (60% in oil), and 0.17 gof (3,3,3-trifluoropropyl)malononitrile, and according to the processdescribed in the Production Example 26, there was obtained 0.21 g of2-(2,3,4,5,6-pentafluorobenzyl)-2-(3,3,3-trifluoropropyl)malononitrile(the present compound (80)).

Yield: 61%;

¹H-NMR (CDCl₃, TMS, δ (ppm)): 2.28–2.34 (2H, m), 2.50–2.68 (2H, m), 3.47(2H, s).

PRODUCTION EXAMPLE 79

Using 0.21 g of 2-chlorobenzyl bromide, 3 ml of N,N-dimethylformamide,0.05 g of sodium hydride (60% in oil), and 0.17 g of(3,3,3-trifluoropropyl)malononitrile, and according to the processdescribed in the Production Example 26, there was obtained 0.22 g of2-(2-chlorobenzyl)-2-(3,3,3-trifluoropropyl)malononitrile (the presentcompound (81)).

Yield: 78%;

¹H-NMR (CDCl₃, TMS, δ (ppm)): 2.28–2.34(2H, m), 2.50–2.62(2H, m),3.53(2H, s), 7.30–7.40(2H, m), 7.47–7.55(2H, m).

PRODUCTION EXAMPLE 80

Using 0.16 g of 3-chlorobenzyl chloride, 3 ml of N,N-dimethylformamide,0.05 g of sodium hydride (60% in oil), and 0.17 g of(3,3,3-trifluoropropyl)malononitrile, and according to the processdescribed in the Production Example 26, there was obtained 0.12 g of2-(3-chlorobenzyl)-2-(3,3,3-trifluoropropyl)malononitrile (the presentcompound (82)).

Yield: 42%;

¹H-NMR (CDCl₃, TMS, δ (ppm)): 2.26–2.31 (2H, m), 2.47–2.62 (2H, m), 3.53(2H, s), 7.26–7.55 (4H, m).

PRODUCTION EXAMPLE 81

Using 0.20 g of 2,4-dichlorobenzyl chloride, 3 ml ofN,N-dimethylformamide, 0.05 g of sodium hydride (60% in oil), and 0.17 gof (3,3,3-trifluoropropyl)malononitrile, and according to the processdescribed in the Production Example 26, there was obtained 0.23 g of2-(2,4-dichlorobenzyl)-2-(3,3,3-trifluoropropyl)malononitrile (thepresent compound (83)).

Yield: 70%;

¹H-NMR (CDCl₃, TMS, δ (ppm)): 2.26–2.31 (2H, m), 2.48–2.63 (2H, m), 3.48(2H, s), 7.35 (1H, dd), 7.47 (1H, d), 7.52 (1H, d).

PRODUCTION EXAMPLE 82

Using 0.19 g of 4-methylbenzyl bromide, 3 ml of N,N-dimethylformamide,0.05 g of sodium hydride (60% in oil), and 0.17 g of(3,3,3-trifluoropropyl)malononitrile, and according to the processdescribed in the Production Example 26, there was obtained 0.20 g of2-(4-methylbenzyl)-2-(3,3,3-trifluoropropyl)malononitrile (the presentcompound (84)).

Yield: 76%;

¹H-NMR (CDCl₃, TMS, δ (ppm)): 2.17–2.27(2H, m), 2.38(3H, 1H),2.48–2.60(2H, m), 3.23(2H, s), 7.21–7.27(4H, m).

PRODUCTION EXAMPLE 83

Using 0.22 g of (4-(trifluoromethyl)benzyl)malononitrile, 3 ml ofN,N-dimethylformamide, 0.05 g of sodium hydride (60% in oil), and 0.31 gof 1-bromo-3-chloropropane, and according to the process described inthe Production Example 1, there was obtained 0.15 g of2-(3-chloropropyl)-2-(4-(trifluoromethyl)benzyl)malononitrile (thepresent compound (85)).

Yield: 26%;

¹H-NMR (CDCl₃, TMS, δ (ppm)): 2.20–2.26(4H, m), 3.26(2H, d), 3.68(2H,dd), 7.51(2H, d), 7.69(2H, d).

PRODUCTION EXAMPLE 84

Using 0.22 g of 2-(4-(trifluoromethyl)benzyl)malononitrile, 3 ml ofN,N-dimethylformamide, 0.05 g of sodium hydride (60% in oil), and 0.33 gof 1-bromo-3-chloro-2-methylpropane, and according to the processdescribed in the Production Example 1, there was obtained 0.19 g of2-(3-chloro-2-methylpropyl)-2-(4-(trifluoromethyl)benzyl)malononitrile(the present compound (86)).

Yield: 30%;

¹H-NMR (CDCl₃, TMS, δ (ppm)): 1.45(3H, d), 1.94(1H, dd), 2.31(1H, dd),2.36–2.43(1H, m), 3.29(2H, s), 3.52(1H, dd), 3.68(1H, dd), 7.53(2H, d),7.69(2H, d).

PRODUCTION EXAMPLE 85

Using 0.22 g of (4-(trifluoromethyl)benzyl)malononitrile, 3 ml ofN,N-dimethylformamide, 0.05 g of sodium hydride (60% in oil), and 0.34 gof 1-bromo-4-chlorobutane, and according to the process described in theProduction Example 1, there was obtained 0.20 g of2-(4-chlorobutyl)-2-(4-(trifluoromethyl)benzyl)malononitrile (thepresent compound (87)).

Yield: 32%;

¹H-NMR (CDCl₃, TMS, δ (ppm)): 1.92–2.14(4H, m), 3.27(2H, s),2.36–2.43(1H, m), 3.29(2H, s), 3.57(2H, dd), 7.52(2H, d), 7.69(2H, d).

PRODUCTION EXAMPLE 86

Using 0.52 g of (3-benzyloxybenzyl)malononitrile, 5 ml ofN,N-dimethylformamide, 0.12 g of sodium hydride (60% in oil), and 0.34 gof 1-bromo-3,3,3-trifluoropropane, and according to the processdescribed in the Production Example 1, there was obtained 0.28 g of2-(3-(benzyloxy)benzyl)-2-(3,3,3-trifluoropropyl)malononitrile (thepresent compound (88)).

Yield: 38%;

¹H-NMR (CDCl₃, TMS, δ (ppm)): 2.05–2.22(2H, m), 2.47–2.59(2H, m),3.24(1H, q), 5.09(2H, s), 6.95–7.26(3H, m), 7.29–7.52(6H, m).

PRODUCTION EXAMPLE 87

Using 0.39 g of 2-(4-methoxybenzyl)malononitrile, 5 ml ofN,N-dimethylformamide, 0.12 g of sodium hydride (60% in oil), and 0.34 gof 1-bromo-3,3,3-trifluoropropane, and according to the processdescribed in the Production Example 1, there was obtained 0.15 g of2-(4-methoxybenzyl)-2-(3,3,3-trifluoropropyl)malononitrile (the presentcompound (89)).

Yield: 27%;

¹H-NMR (CDCl₃, TMS, δ (ppm)): 2.04–2.22(2H, m), 2.46–2.63(2H, m),3.79(1H, q), 3.83(3H, s), 6.92(2H, d), 7.27(2H, d).

The following will describe some production examples for intermediatecompounds as reference production examples.

REFERENCE PRODUCTION EXAMPLE 1

First, 1.00 g of (4-chloro-α-methylbenzylidene)malononitrile of theformula:

was dissolved in 20 ml of diethyl ether, to which a catalytic amount ofcopper (I) iodide was added, and while stirring under ice cooling, asolution of methyl magnesium iodide in diethyl ether (prepared from 0.30g of magnesium, 10 ml of diethyl ether, and 0.86 ml of methyl iodide)was added dropwise, followed by stirring for 30 minutes under icecooling. Then, 10% hydrochloric acid was added to the reaction mixture,which was extracted with ethyl ether. The organic layer was successivelywashed with 10% hydrochloric acid, a saturated aqueous sodium chloridesolution, dried over anhydrous magnesium sulfate, and then concentratedunder reduced pressure. The residue was subjected to silica gel columnchromatography to give 0.74 g of(1-(4-chlorophenyl)-1-methylethyl)malononitrile (the intermediate (2)).

Yield: 69%.

REFERENCE PRODUCTION EXAMPLE 2

First, 1.02 g of (4-chlorobenzylidene)malononitrile was dissolved in 20ml of tetrahydrofuran, to which a catalytic amount of copper (I) iodidewas added, and while stirring under ice cooling, a solution of isopropylmagnesium bromide in tetrahydrofuran (prepared from 0.34 g of magnesium,10 ml of tetrahydrofuran, and 1.46 ml of isopropyl bromide) was addeddropwise, followed by stirring for 30 minutes under ice cooling. Then,10% hydrochloric acid was added to the reaction mixture, which becameacidic and was extracted with ethyl ether. The organic layer wassuccessively washed with 10% hydrochloric acid, a saturated aqueoussodium chloride solution, dried over anhydrous magnesium sulfate, andthen concentrated under reduced pressure. The residue was subjected tosilica gel column chromatography to give 0.66 g of(1-(4-chlorophenyl)-2-methylpropyl)malononitrile (the intermediate (3)).

Yield: 52%.

REFERENCE PRODUCTION EXAMPLE 3

First, 4.44 g of (4-(trifluoromethyl)benzylidene)malononitrile wasdissolved in 20 ml of ethanol, and while stirring at room temperature, asuspension of 0.19 g of sodium borohydride in 5 ml of ethanol was addeddropwise, followed by stirring at room temperature for 30 minutes. Then,10% hydrochloride acid was added to the reaction mixture, which becameacidic and was extracted with diethyl ether. The organic layer wassuccessively washed with 10% hydrochloric acid, a saturated aqueoussodium chloride solution, dried over anhydrous magnesium sulfate, andthen concentrated under reduced pressure. The residue was subjected tosilica gel column chromatography to give 2.30 g of(4-(trifluoromethyl)benzyl)malononitrile (the intermediate (4)).

Yield: 51%.

REFERENCE PRODUCTION EXAMPLE 4

First, 3.00 g of (4-chloro-α-methylbenzylidene)malononitrile wasdissolved in 20 ml of ethanol, and while stirring at room temperature, asuspension of 0.15 g of sodium borohydride in 5 ml of ethanol was addeddropwise, followed by stirring at room temperature for 30 minutes. Then,10% hydrochloride acid was added to the reaction mixture, which wasextracted with diethyl ether. The organic layer was successively washedwith 10% hydrochloric acid, a saturated aqueous sodium chloridesolution, dried over anhydrous magnesium sulfate, and then concentratedunder reduced pressure. The residue was subjected to silica gel columnchromatography to give 1.70 g of (1-(4-chlorophenyl)ethyl)malononitrile(the intermediate (6)).

Yield: 56%.

REFERENCE PRODUCTION EXAMPLE 5

First, 10.0 g of 4-(trifluoromethoxy)benzaldehyde and 3.50 g ofmalononitrile were dissolved in 60 ml of 70% (w/w) aqueous ethanol, towhich a catalytic amount of benzyltrimethylammonium hydroxide was added,and the mixture was stirred at room temperature overnight. Then, asaturated aqueous sodium chloride solution was added to the reactionmixture, which was extracted with ethyl acetate. The organic layer waswashed with a saturated aqueous sodium chloride solution, dried overanhydrous magnesium sulfate, and then concentrated under reducedpressure. The residue was recrystallized from t-butyl methyl ether andhexane to give 9.24 g of (4-(trifluoromethoxy)benzylidene)malononitrile.

Yield: 74%;

¹H-NMR (CDCl₃, TMS, δ (ppm)): 7.37 (2H, d), 7.76 (1H, s), 7.98 (2H, d).

Then, 2.61 g of (4-(trifluoromethoxy)benzylidene)malononitrile wasdissolved in 20 ml of tetrahydrofuran, and while stirring at roomtemperature, a suspension of 0.11 g of sodium borohydride in 5 ml ofethanol was added dropwise, followed by stirring at room temperature for30 minutes. Then, 10% hydrochloric acid was added, and the mixture wasextracted with diethyl ether. The organic layer was successively washedwith 10% hydrochloric acid, a saturated aqueous sodium chloridesolution, dried over anhydrous magnesium sulfate, and then concentratedunder reduced pressure. The residue was subjected to silica gel columnchromatography to give 2.20 g of(4-(trifluoromethoxy)benzyl)malononitrile (the intermediate (7)).

Yield: 83%.

REFERENCE PRODUCTION EXAMPLE 6

Using 1.19 g of (4-(trifluoromethoxy)benzylidene)malononitrile, 20 ml oftetrahydrofuran, a catalytic amount of copper (I) iodide, and a solutionof isopropyl magnesium bromide in tetrahydrofuran (prepared from 0.39 gof magnesium, 10 ml of tetrahydrofuran, and 2.36 g of isopropylbromide), and according to the process described in REFERENCE PRODUCTIONEXAMPLE 2, there was obtained 0.77 g of(1-(4-(trifluoromethoxy)phenyl)-2-methylpropyl)malononitrile (theintermediate (8)).

Yield: 55%.

REFERENCE PRODUCTION EXAMPLE 7

Using 1.19 g of (4-(trifluoromethoxy)benzylidene)malononitrile, 20 ml oftetrahydrofuran, a catalytic amount of copper (1) iodide, and 12.5 ml ofa solution of methyl magnesium bromide in tetrahydrofuran (about 1 M,available from Tokyo Kasei Kogyo Co., Ltd), and according to the processdescribed in REFERENCE PRODUCTION EXAMPLE 2, there was obtained 0.76 gof (1-(4-(trifluoromethoxy)phenyl)ethyl)malononitrile (the intermediate(10)).

Yield: 60%.

REFERENCE PRODUCTION EXAMPLE 8

First, 4.46 g of (3,4-dichlorobenzylidene)malononitrile was dissolved in20 ml of tetrahydrofuran, and while stirring at room temperature, asuspension of 0.19 g of sodium borohydride in 5 ml of ethanol was addeddropwise, followed by stirring at room temperature for 30 minutes. Then,10% hydrochloride acid was added and the mixture was extracted withdiethyl ether. The organic layer was successively washed with 10%hydrochloric acid, a saturated aqueous sodium chloride solution, driedover anhydrous magnesium sulfate, and then concentrated under reducedpressure. The residue was subjected to silica gel column chromatographyto give 3.15 g of (3,4-dichlorobenzyl)malononitrile (the intermediate(12)).

Yield: 70%.

REFERENCE PRODUCTION EXAMPLE 9

Using 4.46 g of (2,4-dichlorobenzylidene)malononitrile, 20 ml oftetrahydrofuran, and a suspension of 0.19 g of sodium borohydride in 5ml of ethanol, and according to the process described in ReferenceProduction Example 8, there was obtained 3.10 g of(2,4-dichlorobenzyl)malononitrile (the intermediate (13)).

Yield: 69%.

REFERENCE PRODUCTION EXAMPLE 10

First, 10.0 g of 4-(trifluoromethylthio)benzaldehyde and 2.92 g ofmalononitrile were dissolved in 50 ml of 70% (w/w) aqueous ethanol, towhich a catalytic amount of benzyltrimethylammonium hydroxide was added,and the mixture was stirred at room temperature overnight. Then, asaturated aqueous sodium chloride solution was added to the reactionmixture, which was extracted with ethyl acetate. The organic layer waswashed with a saturated aqueous sodium chloride solution, dried overanhydrous magnesium sulfate, and then concentrated under reducedpressure. The residue was recrystallized with a solvent systemconsisting of t-butyl methyl ether and hexane to give 10.5 g of(4-(trifluoromethylthio)benzylidene)malononitrile.

Yield: 85%;

¹H-NMR (CDCl₃, TMS, δ (ppm)): 7.78 (1H, s), 7.79 (2H, d), 7.93 (2H, d).

Then, 8.00 g of (4-(trifluoromethylthio)benzylidene)malononitrile and3.35 g of benzaldehyde were dissolved in 320 ml of ethanol, and whilestirring at room temperature, 3.41 g of phenylenediamine was slowlyadded, and the mixture was stirred at room temperature for 5 hours.Then, the reaction mixture was concentrated, 300 ml of t-butyl methylether was added, and insoluble matters were filtered. The filtrate wasconcentrated and the resulting residue was subjected to silica gelchromatography to give 6.22 g of(4-(trifluoromethylthio)benzyl)malononitrile (the intermediate (14)).

Yield: 77%.

REFERENCE PRODUCTION EXAMPLE 11

First, 6.98 g of malononitrile, 681 mg of tetrabutylammonium bromide,and 10 g of 4-bromo-1,1,2-trifluoro-1-butene were mixed, and whilestirring at 0° C. under an atmosphere of nitrogen, 5.92 g of potassiumt-butoxide was slowly added. The mixture was further stirred at roomtemperature for 12 hours. Then, the reaction mixture was poured intowater, followed by extraction with t-butyl methyl ether. The organiclayer was washed with water, a saturated aqueous sodium chloridesolution, dried over anhydrous magnesium sulfate, and then concentratedunder reduced pressure. The residue was subjected to silica gel columnchromatography to give 1.31 g of(3,4,4-trifluoro-3-butenyl)malononitrile (the intermediate (17)).

Yield: 26%.

REFERENCE PRODUCTION EXAMPLE 12

Using 4.00 g of (4-(trifluoromethoxy)benzylidene)malononitrile, 30 ml oftetrahydrofuran, 175 mg of copper (I) bromide dimethyl sulfide complex,and 26 ml of a solution (0.98 M) of vinyl magnesium bromide intetrahydrofuran, and according to the process described in ReferenceProduction Example 2, there was obtained 1.60 g of(1-(4-trifluoromethoxyphenyl))-2-propenylmalononitrile (the intermediate(18)).

REFERENCE PRODUCTION EXAMPLE 13

First, 27.6 g of malononitrile was dissolved in 50 ml ofN,N-dimethylformamide, and 27.6 g of potassium carbonate was added atroom temperature, followed by stirring for 1 hour. Then, a solution of17.7 g of 1-bromo-3,3,3-trifluoropropane dissolved in 20 ml ofN,N-dimethylformamide was added dropwise slowly, followed by stirringfor 1 hour. Then, water was added to the reaction mixture, which wasextracted with diethyl ether. The organic layer was successively washedwith water, a saturated aqueous sodium chloride, dried over anhydrousmagnesium sulfate, and then concentrated under reduced pressure. Theresidue was subjected to silica gel column chromatography to give 11.3 gof (3,3,3-trifluoropropyl)malononitrile (the intermediate (16)).

Yield: 68%.

REFERENCE PRODUCTION EXAMPLE 14

First, 20 ml of tetrahydrofuran was added dropwise slowly to the mixtureof 0.50 g of dihydro tetrakis(triphenylphosphine)ruthenium and 3.00 g of(4-(trifluoromethyl)benzyl)malononitrile under an atmosphere of nitrogen, followed by stirring for 15 minutes. Then, 0.82 g of acrolein wasadded dropwise slowly, followed by stirring for 1 hour at roomtemperature and then the solvent was distilled away. The residue wassubjected to silica gel column chromatography to give 1.58 g of2-(2-formylethyl)-2-(4-(trifluoromethyl)benzyl)malononitrile (theintermediate (19)).

Yield: 42%.

REFERENCE PRODUCTION EXAMPLE 15

First, 0.01 g of sodium borohydride was added to the solution of 0.30 gof 2-(2-formylethyl)-2-(4-(trifluoromethyl)benzyl)malononitrile (theintermediate (19)) in ethanol at 0° C., followed by stirring for 5 hoursat room temperature. Then, water was added to the reaction mixture,which was extracted with ethyl acetate. The organic layer was washedwith a saturated aqueous sodium chloride, dried over anhydrous magnesiumsulfate, and then concentrated under reduced pressure. The residue wassubjected to silica gel column chromatography to give 0.19 g of2-(3-hydroxypropyl)-2-(4-(trifluoromethyl)benzyl)malononitrile (theintermediate (20)).

Yield: 61%.

REFERENCE PRODUCTION EXAMPLE 16

Using 1.42 g of (2,4,6-trifluorobenzyliden)malononitrile, 50 ml ofethanol and 0.08 g of sodium borohydride, and according to the processdescribed in the REFERENCE PRODUCTION EXAMPLE 3, there was obtained 1.29g of (2,4,6-trifluorobenzyl)malononitrile (the intermediate (21)).

Yield: 90%.

REFERENCE PRODUCTION EXAMPLE 17

Using 10.0 g of (3,4-difluorobenzyliden)malononitrile, 200 ml of ethanoland 0.6 g of sodium borohydride, and according to the process describedin the REFERENCE PRODUCTION EXAMPLE 3, there was obtained 8.05 g of(3,4-difluorobenzyl)malononitrile (the intermediate (23)).

Yield: 80%.

REFERENCE PRODUCTION EXAMPLE 18

Using 10.0 g of (2-chloro-4-fluorobenzyliden)malononitrile, 200 ml ofethanol and 0.6 g of sodium borohydride, and according to the processdescribed in the REFERENCE PRODUCTION EXAMPLE 3, there was obtained 0.55g of (2-chloro-4-fluorobenzyl)malononitrile (the intermediate (24)).

Yield: 53%.

REFERENCE PRODUCTION EXAMPLE 19

First, 0.93 g of 3-bromobenzaldehyde and 0.33 g of malononitrile weredissolved in 5 ml of ethanol, to which 1.5 ml of water was added,followed by stirring at room temperature for 4 hours. Then, aftercooling at −5° C., a suspension of 57 mg of sodium borohydride in 3 mlof ethanol was added dropwise, followed by stirring at −5° C. for 30minutes. 10% hydrochloride acid was added to the reaction mixture, whichwas extracted with ethyl acetate. The organic layer was washed withwater, dried over anhydrous magnesium sulfate, and then concentratedunder reduced pressure. The residue was subjected to silica gel columnchromatography to give 0.94 g of (3-bromobenzyl)malononitrile (theintermediate (28)).

Yield: 83%.

REFERENCE PRODUCTION EXAMPLE 20

Using 1.02 g of 2-fluoro-4-bromobenzaldehyde, 0.33 g of malononitrile, 8ml of ethanol, 1.5 ml of water and 57 mg of sodium borohydride, andaccording to the process described in the REFERENCE PRODUCTION EXAMPLE19, there was obtained 1.21 g of (2-fluoro-4-bromobenzyl)malononitrile(the intermediate (29)).

Yield: 95%.

REFERENCE PRODUCTION EXAMPLE 21

Using 1.06 g of 3-(benzyloxy)benzaldehyde, 0.33 g of malononitrile, 8 mlof ethanol, 1.5 ml of water and 57 mg of sodium borohydride, andaccording to the process described in the REFERENCE PRODUCTION EXAMPLE19, there was obtained 1.20 g of (3-(benzyloxy)benzyl)malononitrile (theintermediate (31)).

Yield: 92%.

REFERENCE PRODUCTION EXAMPLE 22

Using 1.0 g of(2,6-dichloro-4-(trifluoromethyl)benzyliden)malononitrile, 20 ml ofethanol and 0.03 g of sodium borohydride, and according to the processdescribed in the REFERENCE PRODUCTION EXAMPLE 3, there was obtained 0.97g of (2,6-dichloro-4-(trifluoromethyl)benzyl)malononitrile (theintermediate (32)).

Yield: 90%.

The intermediate compounds used in the production of the presentcompounds are shown below with the compound numbers and physical data.

Specific examples of the present compounds are shown in Table 1 with thecompound numbers.

TABLE 1 The compounds of formula (Y): (Y)

No. R¹ R² m R³ (R⁵)_(n) R⁶ 1 H H 1 CCl═CH₂ — Cl 2 H H 1 CCl═CH₂ — SCF₃ 3H H 1 CF₃ — H 4 H H 2 CF═CF₂ — H 5 H H 1 CF₂CF₃ — OCF₃ 6 H H 2 CF₃ —C(═O)CH₃ 7 H H 2 CF₃ 2,6-Cl₂ CF₃ 8 H H 2 CF₂CF₃ — CF₃ 9 H H 2 CF₃ — Br10 H H 2 CF₂CF₃ — OCF₃ 11 H H 2 CHF₂ — CF₃ 12 H H 2 CF₃ — H 13 H H 2 CF₃— SCF₃ 14 H H 2 CH₂F — CF₃ 15 H H 2 CF₃ — Cl 16 H H 2 CF₃ — F 17 H H 2CF₃ 2,6-F₂ F 18 H H 2 CF₃ — NO₂ 19 H H 2 CF₃ 3-F F 20 H H 1 CH═CCl₂ — Cl21 H H 2 CF₃ 3-Cl Cl 22 H H 2 CF₃ — CN 23 H H 2 CF₂CF₃ — Cl 24 H H 1CH₂F — Cl 25 H H 1 CF₂CHF₂ — Cl 26 H H 2 CF₃ — I 27 H H 2 CF₃ — CH═CH₂28 H H 1 CH═CCl₂ — OCF₃ 29 H H 1 CH═CBr₂ — OCF₃ 30 H H 2 CF₃ 3-NO₂ CH₃31 H H 2 CF₃ — CH₂CH₃ 32 H H 2 CF₃ 3-OCH₃ H 33 H H 2 CF₃ — C(CH₃)₃ 34 HH 2 CF₃ — SCH₃ 35 H H 2 CF₃ — CH(CH₃)₂ 36 H H 2 CF₃ 3-CF₃ H 37 H H 2 CF₃3-CH₃ H 38 H H 2 CF₃ 2-Cl NO₂ 39 H H 2 CF₃ 3-Cl CF₃ 40 H H 2 CF₃2,3-(OCH₃)₂ H 41 H H 2 CF₃ 2-Cl CF₃ 42 H CH₃ 2 CF₃ — Cl 43 H H 2 CF₃ —CHBrCH₂Br 44 H H 2 CF₃ 2-Cl F 45 H H 2 CF₃ 3-CH₃ NO₂ 46 H H 1 CH₂F — CN47 H H 1 CH₂F — NO₂ 48 H H 1 CH₂═CFCF₃ — CF₃ 49 H H 2 CF═CF₂ — OCF₃ 50 HH 2 CF₃ — OCF₃ 51 H H 1 CH₂F — Br 52 H H 1 CH₂F — OCH₃ 53 H CH₃ 1 CH₂F —Cl 54 H H 2 CF═CF₂ — SCF₃ 55 H H 1 CH═CCl₂ — CF₃ 56 H H 1 CH═CCl₂ — CN57 H CH₃ 2 CF₃ — CF₃ 58 H H 2 CF₃ — CH═CHBr 59 H H 1 CH₂F — F 60 H H 1(E)-CH═CHCl — H 61 H H 1 (Z)-CH═CHCl — H 62 H H 2 CF═CF₂ 2-Cl CF₃ 63 H H1 CH₂Cl 3-Cl H 64 H H 1 CH₂F — CF₃ 65 H H 1 CH₂F 3-Br H 66 H H 2 CF═CF₂2,6-Cl₂ CF₃ 67 H H 1 CH₂F 2-F Br 68 H H 2 CF═CF₂ — CN 69 H H 1 CH₂F 2-BrH 70 H H 2 CF₃ 2-F F 71 H H 2 CF₃ 3,5-F₂ H 72 H H 1 CF₃ — CF₃ 73 H H 2CF═CF₂ — CF₃ 74 H H 2 CF₃ — CF₃ 75 H H 2 CF₃ 2-F H 76 H H 1 CF₂CF₃ — CF₃77 H H 1 CF₂CF₂CF₃ — CF₃ 78 H H 3 CF₃ — CF₃ 79 H H 2 CF₃ 3-F H 80 H H 2CF₃ 2,3,5,6-F₄ F 81 H H 2 CF₃ 2-Cl H 82 H H 2 CF₃ 3-Cl H 83 H H 2 CF₃2-Cl Cl 84 H H 2 CF₃ — CH₃ 85 H H 2 CH₂Cl — CF₃ 86 H H 1 CH(CH₃)CH₂Cl —CF₃ 87 H H 3 CH₂Cl — CF₃ 88 H H 2 CF₃ 3-OCH₂Ph H 89 H H 2 CF₃ — OCH₃ 90H H 2 CF₃ 3-F CF₃ 91 H CH₃ 2 CF₃ 3-F CF₃ 92 H H 2 CF₃ 3-CH₃ CN 93 H H 2CF₃ 3-CF₃ Cl 94 H CH₃ 2 CF₃ 3-CF₃ Cl 95 H H 2 CF₃ 3-Cl NO₂ 96 H H 2 CF₃3-F NO₂ 97 H H 2 CF₃ 3-F CN 98 H CH₃ 2 CF₃ 3-F CN 99 H H 2 CF₃ 3,5-F₂CF₃ 100 H H 2 CF₃ 3-Cl F 101 H CH₃ 2 CF₃ 3-Cl F 102 H H 2 CF₃ 3-Cl F 103H CH₃ 2 CF₃ 3-F Cl 104 H H 2 CF₃ 3,5-Cl₂ Cl 105 H H 2 CF₃ 3,5-F₂ F 106 HCH₃ 2 CF₃ — OCF₃ 107 H CH₃ 2 CF₃ — SCF₃ 108 H H 3 CF₃ — OCF₃ 109 H H 3CF₃ — SCF₃ 110 H H 3 CF₃ — NO₂ 111 H H 3 CF₃ — CN 112 H CH₃ 3 CF₃ — CN113 H H 3 CF₃ — Cl 114 H CH₃ 3 CF₃ — Cl 115 H H 3 CF₃ — F 116 H H 3 CF₃3-Cl CF₃ 117 H CH₃ 3 CF₃ 3-Cl CF₃ 118 H H 3 CF₃ 3-F CF₃ 119 H CH₃ 3 CF₃3-F CF₃ 120 H H 3 CF₃ 3-Cl F 121 H CH₃ 3 CF₃ 3-Cl F 122 H H 3 CF₃ 3-ClCN 123 H H 3 CF₃ 3-Cl Cl 124 H CH₃ 3 CF₃ 3-Cl Cl 125 H H 3 CF₃ 3-F F 126H CH₃ 3 CF₃ 3-F F 127 H H 3 CF₃ 3-CF₃ H 128 H H 2 CF₂CF₃ — OCF₃ 129 H H2 CF₂CF₃ — SCF₃ 130 H H 2 CF₂CF₃ — NO₂ 131 H H 2 CF₂CF₃ — CN 132 H CH₃ 2CF₂CF₃ — CN 133 H H 2 CF₂CF₃ — Cl 134 H CH₃ 2 CF₂CF₃ — Cl 135 H H 2CF₂CF₃ — F 136 H H 2 CF₂CF₃ 3-Cl CF₃ 137 H CH₃ 2 CF₂CF₃ 3-Cl CF₃ 138 H H2 CF₂CF₃ 3-F CF₃ 139 H CH₃ 2 CF₂CF₃ 3-F CF₃ 140 H H 2 CF₂CF₃ 3-Cl F 141H CH₃ 2 CF₂CF₃ 3-Cl F 142 H H 2 CF₂CF₃ 3-Cl CN 143 H H 2 CF₂CF₃ 3-Cl Cl144 H CH₃ 2 CF₂CF₃ 3-Cl Cl 145 H H 2 CF₂CF₃ 3-F F 146 H CH₃ 2 CF₂CF₃ 3-FF 147 H H 2 CF₂CF₃ 3-CF₃ H 148 H CH₃ 2 CF₃ 3-Cl Cl 149 H CH₃ 2 CF₃ 3-F F150 H CH₃ 2 CF₃ 3-Cl CF₃ 151 H CH₃ 2 CF₃ 3-CF₃ Cl 152 H H 2 CF₃ 3-CF₃ Cl153 H CH₃ 2 CF₃ 3-CF₃ H 154 H H 1 CH═CF₂ — CF₃ 155 H H 1 CH═CF₂ — Cl 156H CH₃ 1 CH═CF₂ — F 157 H H 1 CH═CF₂ — CN 158 H H 1 CH═CF₂ — NO₂ 159 HCH(CH₃)₂ 1 CH═CF₂ — SCF₃ 160 H H 1 CH═CF₂ — OCF₃ 161 H H 1 CH═CF₂ 3-ClCl 162 H H 1 CH═CF₂ 3-Cl F 163 H H 1 CH═CF₂ 3-F F 164 H H 1 CH═CF₂ 3-ClCF₃ 165 H H 1 CH═CF₂ 3-F CF₃ 166 H H 2 CH═CF₂ — CF₃ 167 H H 2 CH═CF₂ —Cl 168 H H 2 CH═CF₂ — F 169 H H 2 CH═CF₂ — CN 170 H CH₃ 2 CHCF₂ — NO₂171 H H 2 CHCF₂ — SCF₃ 172 H CH(CH₃)₂ 2 CH═CF₂ — OCF₃ 173 H H 2 CH═CF₂3-Cl Cl 174 H H 2 CH═CF₂ 3-Cl F 175 H H 2 CH═CF₂ 3-F F 176 H H 2 CH═CF₂3-Cl CF₃ 177 H H 2 CH═CF₂ 3-F CF₃ 178 H H 2 CF_(2CH3) — CF₃ 179 H H 2CF_(2CH3) — Cl 180 H H 2 CF_(2CH3) — F 181 H H 2 CF_(2CH3) — CN 182 H H2 CF_(2CH3) — NO₂ 183 H CH₃ 2 CF_(2CH3) — SCF₃ 184 H CH(CH₃)₂ 2CF_(2CH3) — OCF₃ 185 H H 2 CF_(2CH3) 3-Cl Cl 186 H H 2 CF_(2CH3) 3-Cl F187 H H 2 CF_(2CH3) 3-F F 188 H H 2 CF_(2CH3) 3-Cl CF₃ 189 H H 2CF_(2CH3) 3-F CF₃ 190 H H 2 C(CF₃)═CH₂ — CF₃ 191 H H 2 C(CF₃)═CH₂ — Cl192 H H 2 C(CF₃)═CH₂ — F 193 H H 2 C(CF₃)═CH₂ — CN 194 H CH(CH₃)₂ 2C(CF₃)═CH₂ — NO₂ 195 H H 2 C(CF₃)═CH₂ — SCF₃ 196 H CH₃ 2 C(CF₃)═CH₂ —OCF₃ 197 H H 2 C(CF₃)═CH₂ 3-Cl Cl 198 H H 2 C(CF₃)═CH₂ 3-Cl F 199 H H 2C(CF₃)═CH₂ 3-F F 200 H H 2 C(CF₃)═CH₂ 3-Cl CF₃ 201 H H 2 C(CF₃)═CH₂ 3-FCF₃ 202 H H 1 C(CF₃)═CH₂ — CF₃ 203 H H 1 C(CF₃)═CH₂ — Cl 204 H H 1C(CF₃)═CH₂ — F 205 H H 1 C(CF₃)═CH₂ — CN 206 H H 1 C(CF₃)═CH₂ — NO₂ 207H H 1 C(CF₃)═CH₂ — SCF₃ 208 H H 1 C(CF₃)═CH₂ — OCF₃ 209 H H 1 C(CF₃)═CH₂3-Cl Cl 210 H H 1 C(CF₃)═CH₂ 3-Cl F 211 H H 1 C(CF₃)═CH₂ 3-F F 212 H H 1C(CF₃)═CH₂ 3-Cl CF₃ 213 H H 1 C(CF₃)═CH₂ 3-F CF₃ 214 H H 2 CH₂Cl — CF₃215 H H 2 CH₂Cl — CN 216 H H 2 CH₂Cl 3-Cl Cl 217 H H 3 CH₂F — NO₂ 218 HH 3 CH₂F 3-Cl Cl 219 H H 3 CH₂F 3-Cl F 220 H H 3 CH₂F 3-Cl CF₃ 221 HOCH₃ 2 CF₃ — CF₃ 222 H OCH(CH₃)₂ 2 CF₃ — CN 223 H CN 2 CF₃ — Cl

The following will describe some formulation examples wherein partsrepresent parts by weight. The present compounds are designated by theircompound numbers shown in Table 1.

FORMULATION EXAMPLE 1

Nine parts of each of the present compounds (1) to (87) is dissolved in37.5 parts of xylene and 37.5 parts of dimethylformamide, and 10 partsof polyoxyethylene styryl phenyl ether and 6 parts of calciumdodecylbenzenesulfonate are added thereto, followed by well stirring andmixing, to give an emulsifiable concentrate for each compound.

FORMULATION EXAMPLE 2

To 40 parts of each of the present compounds (1) to (87) is added 5parts of Solpol® 5060 (Toho Chemical Industry Co., Ltd.), followed bywell mixing, and 32 parts of Carplex® #80 (synthetic hydrated siliconeoxide fine powder; Shionogi & Co., Ltd.) and 23 parts of 300 meshdiatomaceous earth are added, which is mixed with a mixer to give awettable powder for each compound.

FORMULATION EXAMPLE 3

To 3 parts of each of the present compounds (1) to (87) are added 5parts of synthetic hydrated silicon oxide fine powder, 5 parts of sodiumdodecylbenzenesulfonate, 30 parts of bentonite, and 57 parts of clay,followed by well stirring and mixing, and an appropriate amount of wateris added to this mixture, followed by further stirring, granulation witha granulator, and air drying, to give a granule for each compound.

FORMULATION EXAMPLE 4

First, 4.5 parts of each of the present compounds (1) to (87), 1 part ofsynthetic hydrated silicon oxide fine powder, 1 part of Doriresu B(Sankyo Co., Ltd.) as a flocculant, and 7 parts of clay are well mixedwith a mortar, followed by stirring and mixing with a mixer. To theresulting mixture is added 86.5 parts of cut clay, followed by wellstirring and mixing, to give a dust for each compound.

FORMULATION EXAMPLE 5

Ten parts of each of the present compounds (1) to (87), 35 parts ofwhite carbon containing 50 parts of polyoxyethylene alkyl ether sulfateammonium salt, and 55 parts of water are mixed and pulverized by the wetgrinding method to give a formulation for each compound.

FORMULATION EXAMPLE 6

First, 0.5 parts of each of the present compounds (1) to (87) isdissolved in 10 parts of dichloromethane, which is mixed with 89.5 partsof ISOPAR ®M (isoparaffin; Exxon Chemical Co.) to give an oilformulation for each compound.

FORMULATION EXAMPLE 7

First, 0.1 parts of the present compounds (1) to (79) and 49.9 parts ofNEO-CHIOZOL (Chuo Kasei K.K.) are put into an aerosol can, to which anaerosol valve is attached. Then, 25 parts of dimethyl ether and 25 partsof LPG are filled in the aerosol can, followed by shaking and attachmentof an actuator, to give an oil-based aerosol.

FORMULATION EXAMPLE 8

First, 0.6 parts of each of the present compounds (1) to (79), 0.01parts of BHT, 5 parts of xylene, 3.39 parts of deodorized kerosine, and1 part of an emulsifier (Atmos 300; Atmos Chemical Co.) are mixed tobecome a solution. Then, this solution and 50 parts of distilled waterare filled in an aerosol can, to which a valve part is attached, and 40parts of a propellant (LPG) is filled under pressure through the valvein the aerosol can to give a water-based aerosol.

The following test example will demonstrate that the present compoundsare useful as the active ingredients of pesticide compositions. Thepresent compounds are designated by their compound numbers shown inTable 1.

TEST EXAMPLE 1

Pesticidal Test against Nilaparvata lugens

Each formulation of the compound 2, 5, 7, 8, 9, 10, 11, 12, 13, 15, 16,19, 21, 22, 23, 24, 25, 26, 27, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39,40, 41, 43, 44, 46, 49, 50, 53, 55, 57, 58, 59, 61, 64, 66, 68, 72, 73,74, 76, 78 and 89 obtained according to Formulation Example 5 wasdiluted with water so that the active ingredient concentration came to500 ppm to prepare a test liquid for each compound. And each formulationof the compound 17 and 76 obtained according to Formulation Example 5was diluted with water so that the active ingredient concentration cameto 200 ppm to prepare a test liquid for each compound.

Fifty grams of molding Bonsoru 2 (available from Sumitomo Chemical Co.,Ltd.) was put into a polyethylene cup, and 10 to 15 seeds of rice wereplanted in the polyethylene cup. Then rice plants were grown until thesecond foliage leaves developed and then cut into the same height of 5cm. The test liquid, which had been prepared as described above, wassprayed at the rate of 20 ml/cup onto these rice plants. After the testliquid sprayed onto the rice plants were dried, the polyethylene cupwith the rice plants was placed in a large polyethylene cup and 30first-instar larvae of Nilaparvata lugens (brown planthopper) were setfree in the large polyethylene cup, which was then kept covered and leftin a greenhouse at 25° C. On the 6th day after the release of larvae ofNilaparvata lugens, the number of parasitic Nilaparvata lugens on therice plants was examined.

As a result, in the treatment with each of the compounds describedabove, the number of parasitic pests on the 6th day after the treatmentwas not greater than 3.

TEST EXAMPLE 2

Pesticidal Test against Nilaparvata lugens

Each formulation of the compound 5, 8, 9, 10, 11, 12, 13, 15, 16, 18,19, 21, 22, 23, 27, 31, 33, 34, 36, 37, 39, 40, 41, 44, 49, 50, 57, 68,72, 73, 74, 77 and 89 obtained according to Formulation Example 5 wasdiluted with water so that the active ingredient concentration came to45.5 ppm to prepare a test liquid for each compound. And eachformulation of the compound 17, 26 and 76 obtained according toFormulation Example 5 was diluted with water so that the activeingredient concentration came to 18.2 ppm to prepare a test liquid foreach compound.

Fifty grams of molding Bonsoru 2 (available from Sumitomo Chemical Co.,Ltd.) was put into a polyethylene cup having five holes of 5 mm, and 10to 15 seeds of rice were planted in the polyethylene cup. Then riceplants were grown until the second foliage leaves developed and thepolyethylene cup with the rice plants was placed in a large polyethylenecup containing 55 ml of the test liquid, which had been prepared asdescribed above, was poured. The rice plants were left in a greenhouseat 25° C. for 6 days and then cut into the same height of 5 cm. Thirtyfirst-instar larvae of Nilaparvata lugens (brown planthopper) were setfree in the large polyethylene cup, which was then kept covered and leftin a greenhouse at 25° C. On the 6th day after the release of larvae ofNilaparvata lugens, the number of parasitic Nilaparvata lugens on therice plants was examined.

As a result, in the treatment with each of the compounds describedabove, the number of parasitic pests on the 6th day after the treatmentwas not greater than 3.

TEST EXAMPLE 3

Pesticidal Test against Aphis gossypii

Each formulation of the compound 8, 9, 10, 11, 13, 15, 16, 18, 19, 21,22, 23, 24, 34, 39, 41, 46, 47, 50, 51, 52, 53, 57, 59, 64, 67, 69 and74 obtained according to Formulation Example 5 was diluted with water sothat the active ingredient concentration came to 500 ppm to prepare atest liquid for each compound.

The seeds of cucumber were planted in a polyethylene cup of 90 ml volumefilled with Molding Aisai 1 (available from Katakura Chikkarin Co.,Ltd,) and grown until their first foliage leaves developed. About 30Aphis gossypii (cotton aphid) were made parasitic on the cucumberplants, which was then left for 24 hours. The test liquid was sprayed atthe rate of 20 ml/cup onto the cucumber plants. After the test liquidsprayed onto the plants were dried, the polyethylene cup with thecucumber plants was placed in a large polyethylene cup, which was thenkept covered and left in a greenhouse at 25° C. On the 6th day after theapplication, the number of Aphis gossypii was examined.

As a result, in the treatment with each of the compounds describedabove, the number of survived pests on the 6th day after the treatmentwas not greater than 3.

TEST EXAMPLE 4

Pesticidal Test against Eysarcoris lewisi

Each formulation of the compound 8, 9, 10, 11, 14, 21, 22, 23, 39, 50,74 and 76 obtained according to Formulation Example 1 was diluted withwater so that the active ingredient concentration came to 100 ppm toprepare a test liquid for each compound.

Then, 3 to 5 seeds of peanut were immersed in the test liquid, which hadbeen prepared as described above, for 1 minute. After the test liquidtreated the seeds of peanut was dried with a paper towel, a filter papermoistened with 1 ml of water was placed on a bottom of polyethylene cupand then the seeds of peanut was placed on it. Six to eight adults ofEysarcoris lewisi were set free in the polyethylene cup, which was thenkept covered and left in a greenhouse at 25° C. On the 7th day after therelease of Eysarcoris lewisi, the number of dead pests and moribundpests was examined.

As a result, in the treatment with each of the compounds describedabove, the rate of dead or moribund pests was 100%.

TEST EXAMPLE 5

Pesticidal Test against Leptinotarsa decemlineata

Each formulation of the compound 5, 8, 10, 15, 21, 50, 74, 76 and 78obtained according to Formulation Example 1 was diluted with water sothat the active ingredient concentration came to 1.6 ppm to prepare atest liquid for each compound.

A leaf of eggplant was immersed in the test liquid, which had beenprepared as described above, for 1 minute. After the test liquid treatedthe leaf of eggplant was dried with a paper towel, the leaf of eggplantwas placed in a polyethylene cup of 3 cm in diameter. One second-instarlarvae of Leptinotarsa decemlineata (Colorado potato beetle) were setfree in the polyethylene cup, which was then kept covered and left in agreenhouse at 25° C. This test was done ten times for one compound. Onthe 5th day after the release of Leptinotarsa decemlineata, the numberof dead pests and moribund pests was examined.

As a result, in the treatment with each of the compounds describedabove, the rate of dead or moribund pests was greater than 80%.

TEST EXAMPLE 6

Pesticidal Test against Musca domestica

Each formulation of the compound 4, 5, 7, 8, 9, 10, 11, 12, 13, 14, 15,16, 18, 19, 21, 22, 23, 26, 27, 31, 33, 34, 35, 36, 39, 42, 44, 45, 46,49, 50, 53, 54, 57, 59, 71, 72, 73, 74, 76, 77, 78, 79, 88 and 89obtained according to Formulation Example 5 was diluted with water sothat the active ingredient concentration came to 500 ppm to prepare atest liquid for each compound.

On the bottom of a polyethylene cup of 5.5 cm in diameter was placed afilter paper on the same size, to which the test liquid had beenprepared as described above, was added dropwise in an amount of 0.7 ml,and 30 mg of sucrose as a bait was placed on it. Ten female adults ofMusca domestics (house fly) were set free in the polyethylene cup, whichwas then kept covered. After 24 hours, their survival was examined todetermine the mortality.

As a result, in the treatment with each of the compounds describedabove, it was exhibited the mortality of 100%.

TEST EXAMPLE 7

Pesticidal Test against Blattalla germanica

Each formulation of the compound 4, 5, 6, 7, 8, 9, 10, 11, 13, 15,16,17, 19, 21, 22, 23, 26, 31, 34, 36, 39, 42, 44, 49, 50, 54, 57, 62, 64,70, 72, 73, 74, 77 and 80 obtained according to Formulation Example 5was diluted with water so that the active ingredient concentration cameto 500 ppm to prepare a test liquid for each compound.

On the bottom of a polyethylene cup of 5.5 cm in diameter was placed afilter paper on the same size, to which the test liquid had beenprepared as described above, was added dropwise in an amount of 0.7 ml,and 30 mg of sucrose as a bait was placed on it. Two male adults ofBlattalla germanica (German cockroach) were set free in the polyethylenecup, which was then kept covered. After 6 days, their survival wasexamined to determine the mortality.

As a result, in the treatment with each of the compounds describedabove, it was exhibited the mortality of 100%.

TEST EXAMPLE 8

Pesticidal Test against Cullex pipiens pallens

Each formulation of the compound 1, 2, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13,14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 25, 26, 27, 28, 29, 30, 31, 32,33, 34, 35, 36, 37, 38, 39, 40, 42, 43, 44, 46, 49, 50, 54, 55, 56, 57,59, 62, 64, 66, 68, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82,83, 84, 85, 86, 87, 88 and 89 obtained according to Formulation Example5 was diluted with water so that the active ingredient concentrationcame to 500 ppm to prepare a test liquid for each compound.

In 100 ml of ion-exchanged water, the test liquid had been prepared asdescribed above, was added dropwise in an amount of 0.7 ml. Theconcentration of active ingredient was 3.5 ppm. Twenty final-instarlarvae of Cullex pipiens pallens (common mosquito) were set free in thesolution. After 1 days, their survival was examined to determine themortality.

As a result, in the treatment with each of the compounds describedabove, it was exhibited the mortality of 100%.

TEST EXAMPLE 9

Pesticidal Test against Ctenocephalides felis

Each of the compound 8, 15, 19, 21 and 34 was dissolved in acetone togive a 0.2 ml solution of 0.114% w/w, which was uniformly treated on afilter paper having 3.8cm in diameter, and air-dried. The amount ofactive ingredient was 200 mg/m². The filter paper was filled in a lid ofa 200 ml glass bottle. Twenty adult Ctenocephalides felis (cat flea)were released in the glass bottle, which was followed by covering withthe lid. The glass bottle was upset for making the fleas contact withthe filter paper. After 24 hours, the mortality was examined.

As a result, in the treatment with each of the compounds describedabove, it was exhibited the mortality of 100%.

INDUSTRIAL APPLICABILITY

The present invention makes it possible to effectively control pestssuch as insect pests, acarine pests, and nematode pests.

1. A malononitrile compound of formula (Y):

wherein R¹ and R² are the same or different and independently C₁–C₅(halo)alkyl, C₁–C₅ (halo)alkyloxy, C₂–C₅ (halo)alkenyl, C₂–C₅(halo)alkynyl, hydrogen, or cyano; R³ is C₁–C₃ haloalkyl, C₂–C₄haloalkenyl, or C₂–C₄ haloalkynyl; m is an integer of 1 to 3; R⁵ ishalogen, cyano, nitro, C₁–C₄ (halo)alkyl, C₂–C₄ (halo)alkenyl, C₂–C₄(halo)alkynyl, C₁–C₄ (halo)alkyloxy, C₁–C₄ (halo)alkylthio, C₁–C₄(halo)alkylsulfinyl, C₁–C₄ (halo)alkylsulfonyl, C₁–C₄(halo)alkylcarbonyl, C₁–C₄ (halo)alkyloxycarbonyl, C₁–C₄(halo)alkylcarbonyloxy, benzyloxy, phenyloxy, or phenylthio, in whichthe phenyloxy and phenylthio groups may optionally be substituted withhalogen or C₁–C₃ alkyl; n is an integer of 0 to 4; R⁶ is hydrogen,halogen, cyano, nitro, C₁–C₄ (halo)alkyl, C₂–C₄ (halo)alkenyl, C₂–C₄(halo)alkynyl, C₁–C₄ (halo)alkyloxy, C₁–C₄ (halo)alkylthio, C₁–C₄(halo)alkylsulfinyl, C₁–C₄ (halo)alkylsulfonyl, C₁–C₄(halo)alkylcarbonyl, C₁–C₄ (halo)alkyloxycarbonyl, C₁–C₄(halo)alkylcarbonyloxy, benzyloxy, phenyloxy, or phenylthio, in whichthe phenyloxy and phenylthio groups may optionally be substituted withhalogen or C₁–C₃ alkyl with the proviso that when n is 2 or more, thenR⁵'s are the same or different from each other.
 2. The malononitrilecompound according to claim 1, wherein R⁶ is halogen, cyano, nitro,C₁–C₄ haloalkyl, C₁–C₄ haloalkyloxy or C₁–C₄ haloalkylthio.
 3. Themalononitrile compound according to claim 1, wherein R¹ and R² are bothhydrogen.
 4. The malononitrile compound according to claim 1, wherein R³is fluoromethyl, trifluoromethyl, or 1,2,2-trifluoroethenyl, and m is 1or
 2. 5. The malononitrile compound according to claim 1, wherein R¹ andR² are the same or different and independently C₁–C₃ (halo)alkyl, C₁–C₃(halo)alkyloxy, C₂–C₄ (halo)alkenyl, C₂–C₄ (halo)alkynyl, hydrogen, orcyano; R⁵ and R⁶ are the same or different and independently halogen,cyano, nitro, C₁–C₃ haloalkyl, C₁–C₃ haloalkyloxy, C₁–C₃(halo)alkylthio, C₁–C₃ (halo)alkylsulfinyl, C₁–C₃ (halo)alkylsulfonyl,C₁–C₃ (halo)alkylcarbonyl, or C₁–C₃ halo-alkyloxycarbonyl.
 6. Themalononitrile compound according to claim 5, wherein R³ is C₁–C₅haloalkyl and m is
 1. 7. A pesticide composition comprising themalononitrile compound of claim 1 as active ingredient and a carrier. 8.A pest controlling method comprising applying a pesticidally effectiveamount of the malononitrile compound of claim 1 to pests or habitats ofpests.
 9. The pest controlling method according to claim 8, wherein thepests are insect pests.